U.S. patent application number 15/757062 was filed with the patent office on 2018-11-01 for polyrotaxane, production method therefor, and optical composition containing said polyrotaxane.
The applicant listed for this patent is Tokuyama Corporation. Invention is credited to Junji Momoda, Katsuhiro Mori, Yasutomo Shimizu, Hiromasa Yamamoto.
Application Number | 20180312643 15/757062 |
Document ID | / |
Family ID | 58188815 |
Filed Date | 2018-11-01 |
United States Patent
Application |
20180312643 |
Kind Code |
A1 |
Shimizu; Yasutomo ; et
al. |
November 1, 2018 |
Polyrotaxane, Production Method Therefor, and Optical Composition
Containing said Polyrotaxane
Abstract
The present invention provides an optical composition from which
an optical article having reduced poor appearance such as
cloudiness and optical strain during lens base material production
can be obtained, and when a photochromic compound is added, a
photochromic cured body having excellent photochromism and
mechanical strength can also be formed, and a polyrotaxane used
therefor. The polyrotaxane has a composite molecular structure
formed of an axle molecule and a plurality of cyclic molecules
clathrating the axle molecule, satisfying at least one of (X) and
(Y). (X): A side chain having a secondary or tertiary hydroxyl
group is introduced into at least part of the cyclic molecule of
the polyrotaxane. (Y): A side chain having a group represented by
-A (A is an organic group, and contains at least one hydroxyl
group) is introduced into at least part of the cyclic molecule of
the polyrotaxane, and a pKa of the hydroxyl group of the compound
represented by H-A is 6 or more and less than 14.
Inventors: |
Shimizu; Yasutomo;
(Shunan-shi, JP) ; Mori; Katsuhiro; (Shunan-shi,
JP) ; Momoda; Junji; (Shunan-shi, JP) ;
Yamamoto; Hiromasa; (Shunan-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Tokuyama Corporation |
Shunan-shi |
|
JP |
|
|
Family ID: |
58188815 |
Appl. No.: |
15/757062 |
Filed: |
August 31, 2016 |
PCT Filed: |
August 31, 2016 |
PCT NO: |
PCT/JP2016/075463 |
371 Date: |
March 2, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 65/04 20130101;
G02B 1/04 20130101; C08L 71/02 20130101; C08B 37/0015 20130101;
G02C 7/102 20130101; C08G 18/7642 20130101; C09K 9/02 20130101;
G02C 7/10 20130101; C08G 18/6644 20130101; C08G 18/757 20130101;
C08G 18/242 20130101; C08G 18/283 20130101; C08G 81/02 20130101;
C08G 18/718 20130101; G02B 5/23 20130101; C08G 83/007 20130101;
C08G 18/288 20130101; C08K 5/0041 20130101; C08G 18/3876 20130101;
C08G 18/6484 20130101; C08G 18/778 20130101; C08G 18/7678 20130101;
G02B 1/041 20130101; C08G 18/4018 20130101; C08K 5/0041 20130101;
C08L 75/04 20130101 |
International
Class: |
C08G 83/00 20060101
C08G083/00; C08B 37/16 20060101 C08B037/16; C09K 9/02 20060101
C09K009/02; C08G 65/04 20060101 C08G065/04; C08G 18/77 20060101
C08G018/77; C08G 81/02 20060101 C08G081/02; G02B 1/04 20060101
G02B001/04; G02B 5/23 20060101 G02B005/23; G02C 7/10 20060101
G02C007/10 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 3, 2015 |
JP |
2015-174232 |
Sep 4, 2015 |
JP |
2015-175101 |
Claims
1. A polyrotaxane, comprising a composite molecular structure
formed of an axle molecule and a plurality of cyclic molecules
clathrating the axle molecule, wherein the polyrotaxane satisfies
at least one of requirements (X) and (Y): requirement (X): a side
chain having a secondary or tertiary hydroxyl group is introduced
into at least part of the cyclic molecule of the polyrotaxane; and
requirement (Y): a side chain having a group represented by the
following formula (1): -A (1) (wherein, A is an organic group
having 1 to 10 carbon atoms and contains at least one hydroxyl
group) is introduced into at least part of the cyclic molecule of
the polyrotaxane; and a pKa of a hydroxyl group of a compound
represented by the following formula (2): H-A (2) is 6 or more and
less than 14.
2. The polyrotaxane according to claim 1, satisfying the
requirement (X).
3. The polyrotaxane according to claim 2, wherein a proportion of a
primary hydroxyl group is 50% or less, when the total mole number
of primary, secondary and tertiary hydroxyl groups of the side
chain is taken as 100%.
4. The polyrotaxane according to claim 2, wherein the side chain
having the secondary or tertiary hydroxyl group comprises a
structure represented by the following formula (1): ##STR00015##
[wherein, Q is formed of at least one kind selected from structures
represented by the following formulas (Q-1), (Q-2) and (Q-3):
##STR00016## (wherein, G is a straight-chain alkylene group or
alkenylene group having 1 to 8 carbon atoms; a branched-chain
alkylene group or alkenylene group having 3 to 20 carbon atoms; an
alkylene group or alkenylene group formed by replacement of a part
of the alkylene group or alkenylene group by a --O-- bond, a --NH--
bond, a --SO-- bond or a --SiO-- bond; or an alkylene group formed
by replacement of a part of hydrogen of the alkylene group by at
least one kind selected from the group consisting of a hydroxyl
group, a carboxyl group, an acyl group, a phenyl group, a halogen
atom and an olefin group, and when a plurality of G exist, each G
may be a same group or a different group, and n.sub.1, n.sub.2 and
n.sub.3 are each independently an integer from 1 to 200), and when
Q is formed of two or more kinds selected from the formulas (Q-1),
(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group
or a different group, a total of n.sub.1, n.sub.2 and n.sub.3 is an
integer from 1 to 200, R.sup.1 and R.sup.2 are each independently a
group selected from hydrogen, a straight-chain alkyl group having 1
to 6 carbon atoms and a branched-chain alkyl group having 1 to 6
carbon atoms, excluding a group in which R.sup.1 and R.sup.2 are
simultaneously hydrogen].
5. The polyrotaxane according to claim 2, wherein the side chain
having the secondary or tertiary hydroxyl group comprises a
structure represented by the following formula (1'): ##STR00017##
[wherein, Q is formed of at least one kind selected from structures
represented by the following formulas (Q-1), (Q-2) and (Q-3):
##STR00018## (wherein, G is a straight-chain alkylene group or
alkenylene group having 1 to 8 carbon atoms; a branched-chain
alkylene group or alkenylene group having 3 to 20 carbon atoms; an
alkylene group or alkenylene group formed by replacement a part of
the alkylene group or alkenylene group by a --O-- bond, a --NH--
bond, a --SO-- bond or a --SiO-- bond; or an alkylene group formed
by replacement of a part of hydrogen of the alkylene group by at
least one kind selected from the group consisting of a hydroxyl
group, a carboxyl group, an acyl group, a phenyl group, a halogen
atom and an olefin group, and when a plurality of G exist, each G
may be a same group or a different group, and n.sub.1, n.sub.2,
n.sub.3 are each independently an integer from 1 to 200), and when
Q is formed of two or more kinds selected from the formulas (Q-1),
(Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may be a same group
or a different group, a total of n.sub.1, n.sub.2 and n.sub.3 is an
integer from 1 to 200, X is an alkylene group or alkenylene group
having 2 to 20 carbons, or an alkylene group or alkenylene group
formed by replacement of a part of the alkylene group or alkenylene
group by a --O-- bond or a --NH-- bond; R.sup.3 and R.sup.4 are
each independently selected from hydrogen, a straight-chain alkyl
group having 1 to 6 carbon atoms or a branched-chain alkyl group
having 1 to 6 carbon atoms, excluding a group in which R.sup.3 and
R.sup.4 are simultaneously hydrogen; and R.sup.5 is carbon or
sulfur].
6. The polyrotaxane according to claim 1, satisfying the
requirement (Y).
7. The polyrotaxane according to claim 6, wherein a proportion of a
hydroxyl group having a pKa of less than 6 or 14 or more is 50% or
less, when the total mole number of the hydroxyl groups of the side
chain is taken as 100%.
8. The polyrotaxane according to claim 6, wherein a side chain
represented by the following formula (3) is introduced into at
least part of the cyclic molecule: -Q-A (3) [wherein, Q is formed
of at least one kind selected from structures represented by the
following formulas (Q-1), (Q-2) and (Q-3): ##STR00019## (wherein, G
is a straight-chain alkylene group or alkenylene group having 1 to
8 carbon atoms; a branched-chain alkylene group or alkenylene group
having 3 to 20 carbon atoms; an alkylene group or alkenylene group
formed by replacement of a part of the alkylene group or alkenylene
group by a --O-- bond, a --NH-- bond, a --SO-- bond or a --SiO--
bond, or an alkylene group formed by replacement of a part of
hydrogen of the alkylene group by at least one kind selected from
the group consisting of a carboxyl group, an acyl group, a phenyl
group, a halogen atom and an olefin group, and when a plurality of
G exist, each G may be a same group or a different group, and
n.sub.1, n.sub.2 and n.sub.3 are each independently an integer from
1 to 200), and when Q is formed of two or more kinds selected from
the formulas (Q-1), (Q-2) and (Q-3), G constituting (Q-1) to (Q-3)
may be a same group or a different group, a total of n.sub.1,
n.sub.2 and n.sub.3 is an integer from 1 to 200, and A is an
organic group having 1 to 10 carbon atoms, and contains at least
one hydroxyl group].
9. The polyrotaxane according to claim 6, wherein a side chain
represented by the following formula (3') is introduced into at
least part of the cyclic molecule: ##STR00020## [wherein, Q is
formed of at least one kind selected from structures represented by
the following formulas (Q-1), (Q-2) and (Q-3): ##STR00021##
(wherein, G is a straight-chain alkylene group or alkenylene group
having 1 to 8 carbon atoms; a branched-chain alkylene group or
alkenylene group having 3 to 20 carbon atoms; an alkylene group or
alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond, a --NH-- bond, a --SO--
bond or a --SiO-- bond; or an alkylene group formed by replacement
of a part of hydrogen of the alkylene group by at least one kind
selected from the group consisting of a carboxyl group, an acyl
group, a phenyl group, a halogen atom and an olefin group, and when
a plurality of G exist, each G may be a same group or a different
group, and n.sub.1, n.sub.2 and n.sub.3 are each independently an
integer from 1 to 200), and when Q is formed of two or more kinds
selected from the formulas (Q-1), (Q-2) and (Q-3), G constituting
(Q-1) to (Q-3) may be a same group or a different group, a total of
n.sub.1, n.sub.2 and n.sub.3 is an integer from 1 to 200, and
R.sup.6 is carbon or sulfur, X is an alkylene group or alkenylene
group having 2 to 20 carbons; or an alkylene group or alkenylene
group formed by replacement of a part of the alkylene group or
alkenylene group by a --O-- bond or a --NH-- bond, and A is an
organic group having 1 to 10 carbon atoms and contains at least one
hydroxyl group].
10. The polyrotaxane according to claim 1, wherein a ring contained
in the cyclic molecule of the polyrotaxane is a cyclodextrin
ring.
11. The polyrotaxane according to claim 1, wherein the axle
molecule threading through an inside of the ring of the cyclic
molecule has a chain structure having bulky groups at both ends, a
chain portion is formed of polyethylene glycol, and the bulky
groups at both ends each is an adamantyl group.
12. An optical composition, comprising the polyrotaxane according
to claim 1.
13. The optical composition according to claim 12, comprising a
compound (B) having two or more groups of at least one kind of
group selected from an isocyanate group and an isothiocyanate group
in one molecule.
14. The optical composition according to claim 12, comprising an
iso(thio)cyanate reactive group-containing compound (C).
15. The optical composition according to claim 12, comprising a
photochromic compound (D).
16. A production method for the polyrotaxane according to claim 2,
comprising: reacting, with a compound represented by the following
formula (2), a polyrotaxane having a composite molecular structure
formed of an axle molecule and a plurality of cyclic molecules
clathrating the axle molecule, and the polyrotaxane in which a side
chain having a primary hydroxyl group is introduced into at least
part of the cyclic molecule of the polyrotaxane: ##STR00022##
(wherein, X is an alkylene group or alkenylene group having 2 to 20
carbons, or an alkylene group or alkenylene group formed by
replacement of a part of the alkylene group or alkenylene group by
a --O-- bond or a --NH-- bond; Z is a group selected from the group
consisting of the following formulas Z-1 to Z-9; R.sup.3 and
R.sup.4 are each independently selected from hydrogen, a
straight-chain alkyl group having 1 to 6 carbon atoms or a
branched-chain alkyl group having 1 to 6 carbon atoms, excluding a
group in which R.sup.3 and R.sup.4 are simultaneously hydrogen; and
R.sup.5 is carbon or sulfur): ##STR00023##
17. The production method for the polyrotaxane according to claim
6, comprising: reacting, with a (thio)isocyanate compound
represented by the following formula (4) in which a hydroxyl group
is protected, a polyrotaxane having a composite molecular structure
formed of an axle molecule and a plurality of cyclic molecules
clathrating the axle molecule, and the polyrotaxane having a side
chain having a primary hydroxyl group a pKa of which is 14 or more
is introduced into at least part of the cyclic molecule of the
polyrotaxane: [Formula 10] O.dbd.R.sup.6.dbd.N--X-T-O--Z (4)
[wherein, R.sup.6 is carbon or sulfur, X is an alkylene group or
alkenylene group having 2 to 20 carbons, or an alkylene group or
alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond or a --NH-- bond,
wherein, T is a group selected from the group consisting of the
following formulas (T-1) and (T-2): ##STR00024## (wherein, R.sup.7
is a group selected from the group consisting of a hydrocarbon
group having 1 to 4 carbon atoms, a halogen atom, a nitro group, an
acyl group, a methylsulfonyl group, a trifluoromethyl group, a
cyano group and a carboxyl group; p is an integer from 0 to 4; and
when the number of R.sup.7 is two or more, each may be a different
group from each other; and R.sup.8 is a trifluoromethyl group or
hydrogen), and wherein, Z is a group selected from the group
consisting of the following formulas Z-1 to Z-9]: ##STR00025##
Description
TECHNICAL FIELD
[0001] The present invention relates to a new polyrotaxane and a
production method therefor, and an optical composition containing
the polyrotaxane.
BACKGROUND ART
[0002] A polyrotaxane has a specific structure of having a cyclic
molecule, and a straight-chain molecule threaded through the cyclic
molecule in a skewered manner, and blocking groups arranged at both
ends of the straight-chain molecule to prevent the cyclic molecule
from being separated from the straight-chain molecule. In this
polyrotaxane, the cyclic molecule can move on the straight-chain
molecule relatively. Therefore, the polyrotaxane has various
characteristics, particularly, excellent mechanical
characteristics, and is expected to be applied and developed in
various manners, and has also been used in an optical material such
as a contact lens (see Patent literature 1), or the like.
Meanwhile, in many optical materials, plastic lenses are used, and
lighter in weight, harder to break and dyeable in comparison with
inorganic lenses, and therefore have been widely used rapidly in
every industrial field in recent years. One of the fields is a
field of an eyeglass lens. The eyeglass lens is required to satisfy
many functions such as transparency, excellent durability, easy
dyeability, and resin strength enough to withstand processing, and
various resin materials for lenses have been developed and used so
far. Moreover, one of kinds of the eyeglass lenses is a
photochromic eyeglass lens. The photochromic eyeglass lens means a
material which is immediately colored in an outdoor place where the
material is irradiated with light including ultraviolet rays such
as sunlight to function as sunglasses, and in an indoor place where
the material is not irradiated with such light, the material is
faded to function as ordinary transparent eyeglasses. A demand
therefor has increasingly grown in recent years.
[0003] In order to provide the optical material with photochromism,
a photochromic compound is generally used in combination with a
plastic material. Specifically, the following means are known: (a)
a method for dissolving a photochromic compound into a
polymerizable monomer, and polymerizing the resulting mixture to
directly shape an optical material such as a lens, which method is
called a kneading method; (b) a method for providing, on a surface
of a plastic molded product such as a lens, a resin layer into
which a photochromic compound is dispersed, by coating or cast
polymerization, which method is called a lamination method; and (c)
a method for bonding two optical sheets with an adhesive layer
formed by an adhesive material resin into which a photochromic
compound is dispersed, which method is called a binder method.
[0004] Incidentally, the optical material such as an optical
article provided with the photochromism is further required to
satisfy the characteristics as described below.
[0005] (I) A degree of coloring (initial coloring) in a visible
light region before being irradiated with ultraviolet rays should
be low.
[0006] (II) A degree of coloring (color optical density) upon being
irradiated with ultraviolet rays should be high.
[0007] (III) A rate (color fading rate) from stopping irradiation
with ultraviolet rays to return to an original state should be
high.
[0008] (IV) Durability against repetitive reversible action of
color development and color fading should be satisfactory.
[0009] (V) Storage stability should be high.
[0010] (VI) The optical material should be easily shaped into
various shapes.
[0011] (VII) Photochromism should be provided without causing
reduction of mechanical strength.
[0012] Accordingly, also upon producing the optical material having
photochromism or the like by using the means (a) to (c) described
above, various proposals have been made so that the requirements as
described above may be satisfied. With regard to the color optical
density, the color fading rate or the like, however, development of
superb photochromism has been required in a current status.
[0013] For example, the kneading method described above has an
advantage of capability of producing a photochromic plastic lens in
bulk and at a low cost by using a glass mold, in which most of the
photochromic plastic lenses are currently produced using this
method.
[0014] In the kneading method, however, sufficient strength is
required for a lens base material. Therefore, it is necessary to
enhance mechanical strength of a matrix resin in which the
photochromic compound is dispersed. Therefore, it becomes difficult
to develop excellent photochromism. More specifically, a degree of
freedom of molecules in the photochromic compound existing in the
matrix resin is reduced, and therefore a photochromic reversible
reaction is adversely affected.
[0015] With regard to such a kneading method, for example, Patent
literature 2 describes a technique on adding a photochromic
compound to a monomer composition containing an isocyanate monomer
and a thiol monomer. Moreover, Patent literature 3 discloses a
photochromic curable composition containing a specific
(meth)acrylic polymerizable monomer and a photochromic
compound.
[0016] Photochromic lenses shaped by allowing polymerization curing
of these compositions, however, are unsatisfactory in view of
photochromic characteristics, while the mechanical strength is
high.
[0017] On the other hand, in the lamination method or the binder
method, the photochromism is developed in a thinner layer formed on
surfaces of various base materials in comparison with the kneading
method described above. Therefore, in order to develop the color
optical density equivalent to the density according to the kneading
method, the photochromic compound is required to be dissolved
thereinto with a high concentration. In the above case, such
problems have remained as insufficiency of solubility and
occurrence of precipitation during storage depending on a kind of
the photochromic compound. Moreover, the layer in which the
photochromism is developed is thin, and therefore durability of the
photochromic compound has been deteriorated in several cases.
[0018] For example, Patent literature 4 discloses a method for
coating a photochromic curable composition on a plastic lens by
spin coating or the like to allow photocuring of the resulting
material to form a photochromic coating layer (This lamination
method is also called a coating method.).
[0019] Moreover, Patent literature 5 discloses a method for forming
a photochromic layer by securing a space between a plastic lens and
a glass mold by using a member such as an elastomer gasket, a
pressure-sensitive adhesive tape or a spacer, and flowing a
photochromic curable composition into the space to allow
polymerization curing thereof (hereinafter, also called two-step
polymerization method).
[0020] Further, Patent literature 6 discloses a production method
for a laminated sheet prepared by bonding a transparent carbonate
sheet therewith by a polyurethane resin adhesive layer containing a
photochromic compound (binder method).
[0021] Also in all the methods in Patent literature 4 to 6,
however, the photochromism is developed in the thin layer in which
the photochromic compound is blended. Therefore, when the
photochromic compound having low solubility is used, the color
optical density tends to be reduced, and further the durability of
the photochromic compound has been also deteriorated in several
cases.
[0022] Patent literature 7 discloses a lamination method for
forming a photochromic coating layer by coating a photochromic
urethane curable composition composed of polyol, isocyanate and the
like on a plastic lens by spin coating or the like to allow thermal
curing thereof. Also in this method, however, sufficient color
optical density is unable to be secured.
[0023] As an art for solving the problems described above, Patent
literature 8 discloses a photochromic composition consisting of a
polyrotaxane having a composite molecular structure formed of an
axle molecule and a plurality of cyclic molecules clathrating the
axle molecule, and having a side chain containing a hydroxyl group
in a part of the cyclic molecule, a polyisocyanate monomer and a
photochromic compound. In the photochromic composition, both high
mechanical strength caused by a urethane bond by incorporating the
polyrotaxane thereinto, and excellent photochromism (color optical
density and a color fading rate) by existence of a free space
formed by bonding of the polyrotaxane to a part of the polyurethane
are satisfied (see Patent literature 8).
CITATION LIST
Patent Literature
[0024] Patent literature 1: WO 2005/095493 A
[0025] Patent literature 2: WO 2012/176439 A
[0026] Patent literature 3: WO 2009/075388 A
[0027] Patent literature 4: WO 2011/125956 A
[0028] Patent literature 5: WO 2003/011967 A
[0029] Patent literature 6: WO 2013/099640 A
[0030] Patent literature 7: WO 2001/055269 A
[0031] Patent literature 8: WO 2015/068798 A
SUMMARY OF THE INVENTION
Technical Problem
[0032] Patent literature 8 above describes evaluation results
indicating a level having substantial no problem on moldability
(optical strain and cloudiness). When an evaluation with higher
accuracy is conducted, however, the moldability has become
insufficient in several cases. Moreover, when various lens shapes
have been evaluated in a similar manner, in particular, a problem
of moldability has become significant in the case of a thick lens,
and room for further improvement has remained.
[0033] Accordingly, an object of the present invention is to
provide an optical composition from which an optical article having
reduced poor appearance such as cloudiness and optical strain
during producing a lens base material can be obtained, and when a
photochromic compound is added thereto, a photochromic cured body
having good photochromism and mechanical strength in addition
thereto can be formed, and an object of the present invention is
also to provide a production method therefor, and a new
polyrotaxane used for the optical composition.
Solution to Problem
[0034] The present inventors have diligently continued to conduct
study in order to solve the problems described above. As a result,
the present inventors have found out that, when a polymerizable
group reacting with an iso(thio)cyanate group of a polyrotaxane is
a primary hydroxyl group, reactivity with the iso (thio) cyanate
group is excessively high, and therefore poor performance is easily
caused. Moreover, the present inventors have found that the poor
performance is caused in many cases, when a pKa of a compound
having a hydroxyl group corresponding to an organic group having
the hydroxyl group is less than 6 or 14 or more. The present
inventors have found out that, when the pKa of the hydroxyl group
reacting with the iso(thio)cyanate group of the polyrotaxane is 14
or more, the reactivity with the iso(thio)cyanate group is
excessively high, and therefore the poor performance is easily
caused. More specifically, the present inventors have obtained
findings in which, if one molecule of the polyrotaxane has a high
molecular weight of several hundred thousands or more, and
therefore viscosity of the optical composition becomes high, and
the reaction heterogeneously progresses, phase separation with
other monomers is easily caused, and poor moldability is easily
caused. Moreover, the present inventors have obtained findings in
which, in the case of the hydroxyl group the pKa of which is less
than 6, the reactivity with the iso(thio)cyanate is excessively
low, and therefore the hydroxyl group exists in the form of an
unpolymerized monomer, and thus the reaction heterogeneously
progresses, and the phase separation and the poor moldability are
easily caused.
[0035] More specifically, if the reactivity is excessively high
upon obtaining the optical article such as the plastic lens, a
polymerization reaction locally progresses and a molded body
becomes heterogeneous, and therefore a stria causing the optical
strain is conceivably formed. Moreover, when the polymerization is
unable to be controlled and a large quantity of polymerization heat
that does not follow polymerization conditions is produced, the
stria is conceivably formed also by occurrence of convection.
Further, the present inventors have found that the polymerization
reaction locally progresses and the molded body becomes
heterogeneous, and therefore a polyrotaxane-rich oligomer is
formed, and the phase separation is caused by such an oligomer, and
thus cloudiness is caused.
[0036] Accordingly, as one aspect for reducing the reactivity, the
present inventors have succeeded in solving such problems by using
a new polyrotaxane having a secondary or tertiary hydroxyl group in
a side chain introduced into a cyclic molecule to reduce the
reactivity of the polyrotaxane with iso(thio)cyanate, and have
completed the present invention.
[0037] Moreover, as another aspect for reducing the reactivity, the
present inventors have succeeded in solving such problems by using
a new polyrotaxane having a hydroxyl group a pKa of which is 6 or
more and less than 14 in a side chain introduced into a cyclic
molecule to reduce the reactivity of the polyrotaxane with
iso(thio)cyanate, and also to keep the polyrotaxane reactable with
the iso(thio)cyanate, and have completed the present invention.
[0038] More specifically, the present invention relates to a
polyrotaxane having a composite molecular structure formed of an
axle molecule and a plurality of cyclic molecules clathrating the
axle molecule, and satisfying at least one of requirements (X) and
(Y), and also relates to a production method therefor and an
optical composition containing the polyrotaxane:
[0039] requirement (X): a side chain having a secondary or tertiary
hydroxyl group is introduced into at least part of the cyclic
molecule of the polyrotaxane; and
[0040] requirement (Y): a side chain having a group represented by
the following formula (1):
-A (1)
[0041] (where, A is an organic group having 1 to 10 carbon atoms
and contains at least one hydroxyl group) is introduced into at
least part of the cyclic molecule of the polyrotaxane; and a pKa of
a hydroxyl group of a compound represented by the following formula
(2):
H-A (2)
is 6 or more and less than 14.
Advantageous Effects of Invention
[0042] An optical composition in which a polyrotaxane satisfying at
least one of requirements (X) and (Y) is used as the polyrotaxane
to suppress moldability and cloudiness, as indicated in Examples
described later. Thus, an optical article having good moldability
and high mechanical strength can be produced with a sufficient
yield. Further, upon adding a photochromic compound to the optical
composition to produce a photochromic lens, the photochromic lens
also having excellent photochromism (color optical density and a
color fading rate) can be produced.
[0043] In the present invention, the polyrotaxane satisfying the
requirement (X) is used to reduce the reactivity with the
iso(thio)cyanate in comparison with a primary hydroxyl group. Thus,
polymerization can be controlled and the moldability and the
cloudiness described above can be suppressed. Further, the
polyrotaxane has the side chain. Thus, a crosslinking structure can
be formed, and excellent mechanical strength can be obtained as
well.
[0044] In the present invention, the polyrotaxane satisfying the
requirement (Y) is used to suppress the reactivity with the
iso(thio)cyanate. Thus, a rate of polymerization can be adjusted
and the moldability and the cloudiness described above can be
suppressed. Further, the polyrotaxane has the side chain. Thus, the
crosslinking structure can be formed, and therefore the excellent
mechanical strength can be obtained as well.
[0045] Further, also upon adding the photochromic compound thereto
to produce a photochromic optical article, excellent photochromic
characteristics can be developed by using the polyrotaxane
according to the present invention. More specifically, the cyclic
molecule of the polyrotaxane is formed to be slidable on the axle
molecule. Therefore, a space is formed around the cyclic molecule.
A reversible structural change of the photochromic compound is
immediately caused by this space. As a result, the color fading
rate and the color optical density are improved. Further, the
reversible structural change of the photochromic compound existing
in the vicinity of a highly flexible side chain can be further
immediately caused by introducing the cyclic molecule in which the
side chain is introduced thereinto.
BRIEF DESCRIPTION OF DRAWINGS
[0046] FIG. 1 is a schematic diagram showing a molecular structure
of a polyrotaxane used in the present invention.
DESCRIPTION OF EMBODIMENTS
[0047] A polyrotaxane according to the present invention has a
composite molecular structure formed of an axle molecule and a
plurality of cyclic molecules clathrating the axle molecule, and
satisfies at least one of requirements (X) and (Y); moreover, an
optical composition according to the present invention contains the
polyrotaxane according to the present invention:
[0048] requirement (X): a side chain having a secondary or tertiary
hydroxyl group is introduced into at least part of the cyclic
molecule of the polyrotaxane; and
[0049] requirement (Y): a side chain having a group represented by
the following formula (1):
-A (1)
[0050] (where, A is an organic group having 1 to 10 carbon atoms
and contains at least one hydroxyl group) is introduced into at
least part of the cyclic molecule of the polyrotaxane; and a pKa of
a hydroxyl group of a compound represented by the following formula
(2):
H-A (2)
is 6 or more and less than 14.
[0051] Hereinafter, each component structuring the present
invention will be described.
[0052] In addition, unless otherwise specified herein, as described
above, the pKa of the hydroxyl group refers to the pKa of the
hydroxyl group when a compound H-A represented by the formula (2)
is formed by substituting, for hydrogen, an atom in a bonding site
at which the group represented by the formula (1) in the
polyrotaxane according to the present invention is bonded with the
side chain.
[0053] In addition, the polyrotaxane having the composite molecular
structure formed of the axle molecule and the plurality of cyclic
molecules clathrating the axle molecule and satisfying the
requirement (X) is also described as the polyrotaxane according to
Aspect I; and the polyrotaxane having the composite molecular
structure formed of the axle molecule and the plurality of cyclic
molecules clathrating the axle molecule and satisfying the
requirement (Y) is also described as the polyrotaxane according to
Aspect II. Moreover, the polyrotaxane according to the present
invention is also described as the polyrotaxane (A).
[0054] As shown in FIG. 1, the polyrotaxane is shown by "1" as a
whole. A polyrotaxane molecule has a composite molecular structure
formed of a chain axle molecule "2" and a cyclic molecule "3". More
specifically, a plurality of cyclic molecules "3" clathrates the
chain axle molecule "2" and the axle molecule "2" threads through
an inside of a ring of the cyclic molecule "3". Accordingly, the
cyclic molecule "3" can freely slide on the axle molecule "2", but
bulky end groups "4" are formed at both ends of the axle molecule
"2", in which the cyclic molecule "3" is prevented from being
dethreaded from the axle molecule "2".
[0055] As described above, such a cyclic molecule "3" of the
polyrotaxane is formed to be slidable on the axle molecule "2".
Therefore, when a photochromic cured body including the
photochromic compound is produced, a space is formed around the
cyclic molecule, and a reversible structural change of the
photochromic compound is immediately caused by this space. As a
result, a color fading rate and color optical density are
improved.
[0056] <Polyrotaxane in which a Side Chain Having a Secondary or
Tertiary Hydroxyl Group is Introduced into at Least Part of a
Cyclic Molecule (Polyrotaxane According to Aspect 1)>
[0057] In the polyrotaxane according to Aspect 1, a side chain "5"
having a secondary or tertiary hydroxyl group is introduced into at
least part of a cyclic molecule.
[0058] Moreover, in the present invention, the polyrotaxane may
have a primary hydroxyl group, in addition to the secondary or
tertiary hydroxyl group, in the side chain. From a viewpoint of
moldability, however, when the total mole number of the primary,
secondary, and tertiary hydroxyl groups in the side chain is taken
as 100%, a proportion of the primary hydroxyl group is preferably
50% or less.
[0059] In the polyrotaxane according to Aspect 1, such a side chain
"5" having the secondary or tertiary hydroxyl group is introduced
into the ring to facilitate to react the iso (thio) cyanate
compound, while the polymerization with the iso(thio)cyanate
compound or the like is controlled, to be described later, and an
optical article having improved moldability can be obtained.
Moreover, a proper space can be further reliably formed between
adjacent axle molecules, a clearance in which a reversible reaction
of the photochromic compound molecule is allowable can be reliably
secured, and excellent photochromism can be conceivably developed.
Further, such a side chain "5" causes formation of a crosslinking
structure in the polyrotaxane. Thus, mechanical strength of the
photochromic cured body formed using the optical composition
according to the present invention can be improved.
[0060] <Polyrotaxane in which a Side Chain Having a Group
Represented by the Formula (1), a pKa of a Hydroxyl Group being 6
or More and Less than 14, is Introduced into at Least Part of an
End of the Side Chain of a Cyclic Molecule (Polyrotaxane According
to Aspect II)>
[0061] In the polyrotaxane according to Aspect II, in which a side
chain "5" being characterized in that the side chain having the
group represented by the formula (1), the pKa of the hydroxyl group
being 6 or more and less than 14, is introduced thereinto is
introduced into at least part of the cyclic molecule.
[0062] Moreover, in the present invention, the polyrotaxane may
have the hydroxyl group the pKa of which is less than 6 or 14 or
more in the side chain. From the viewpoint of the moldability,
however, when the total mole number of the hydroxyl groups in the
side chain is taken as 100%, a proportion of the hydroxyl group the
pKa of which is less than 6 or 14 or more is preferably 50% or
less.
[0063] In the polyrotaxane according to Aspect II, such a side
chain "5" having the hydroxyl group the pKa of which is 6 or more
and less than 14 is introduced into the ring to facilitate to react
the iso(thio)cyanate compound, while the polymerization with the
iso(thio)cyanate compound is controlled, to be described later, and
the optical article having improved moldability can be obtained.
Moreover, the proper space can be further reliably formed between
the adjacent axle molecules, the clearance in which the reversible
reaction of the photochromic compound molecule is allowable can be
reliably secured, and the excellent photochromism can be
conceivably developed. Further, such a side chain "5" causes
formation of the crosslinking structure in the polyrotaxane. Thus,
the mechanical strength of the photochromic cured body formed using
the optical composition according to the present invention can be
improved.
[0064] In the polyrotaxane according to the present invention, as
the axle molecule, various materials can be used. For example, a
chain portion may have a straight chain or branched chain, as long
as the chain portion can thread through the ring of the cyclic
molecule, and is generally formed of a polymer.
[0065] Specific examples of the polymer that forms such a chain
portion of the axle molecule include: polyvinyl alcohol; polyvinyl
pyrrolidone; a cellulose-based resin (such as carboxymethyl
cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose);
polyacrylamide; polyethylene oxide; polyethylene glycol;
polypropylene glycol; polyvinyl acetal; polyvinyl methyl ether;
polyamine; polyethyleneimine; casein; gelatin; starch; an
olefin-based resin (such as polyethylene and polypropylene);
polyester; polyvinyl chloride; a styrene-based resin (polystyrene
and an acrylonitrile-styrene copolymer resin); an acrylic resin
(such as poly(meth)acrylate, polymethyl methacrylate, polymethyl
acrylate and an acrylonitrile-methyl acrylate copolymer resin);
polycarbonate; polyurethane; a vinyl chloride-vinyl acetate
copolymer resin; polyvinyl butyral; polyisobutylene;
polytetrahydrofuran; polyaniline; an
acrylonitrile-butadiene-styrene copolymer (ABS resin); polyamide
(such as nylon); polyimide; polydiene (such as polyisoprene and
polybutadiene); polysiloxane (such as polydimethylsiloxane);
polysulfone; polyimine; polyacetic anhydride; polyurea;
polysulfide; polyphosphazene; polyketone; polyphenylene; and
polyhaloolefin. These polymers may be appropriately copolymerized
or may be modified.
[0066] A preferred material as the polymer that forms the chain
portion in the present invention include: polyethylene glycol;
polyisoprene; polyisobutylene; polybutadiene; polypropylene glycol;
polytetrahydrofuran; polydimethylsiloxane; polyethylene;
polypropylene; polyvinyl alcohol; or polyvinyl methyl ether, and
most preferably polyethylene glycol.
[0067] Further, the bulky groups to be formed at both ends of the
chain portion are not particularly limited, as long as the group
prevents the cyclic molecule from being dethreaded from the axle
molecule. From a viewpoint of bulkiness, however, specific examples
thereof can include an adamantyl group, a trityl group, a
fluoresceinyl group, a dinitrophenyl group and a pyrenyl group. In
particular, in view of ease of introduction, specific examples
thereof can include an adamantyl group.
[0068] A molecular weight of the axle molecule described above is
not particularly limited, but if the molecular weight is
excessively large, compatibility with other components tends to be
deteriorated, and if the molecular weight is excessively low,
mobility of the cyclic molecule tends to be reduced and the
photochromism tends to be reduced. From such a viewpoint, a weight
average molecular weight (Mw) of the axle molecule is in the range
preferably from 1,000 to 100,000, particularly from 5,000 to
80,000, and particularly preferably from 10,000 to 50,000.
[0069] Moreover, the cyclic molecule has a ring having a size
capable of clathrating the axle molecule as described above, and
specific examples of such a ring can include a cyclodextrin ring, a
crown ether ring, a benzocrown ring, a dibenzocrown ring and a
dicyclohexanocrown ring, and a cyclodextrin ring is particularly
preferable.
[0070] In addition, the cyclodextrin ring has an .alpha.-form (ring
inner diameter: 0.45 to 0.6 nm), a .beta.-form (ring inner
diameter: 0.6 to 0.8 nm) and a .gamma.-form (ring inner diameter:
0.8 to 0.95 nm). In the present embodiment, however, an
.alpha.-cyclodextrin ring and a .gamma.-cyclodextrin ring are
particularly preferable, and an .alpha.-cyclodextrin ring is most
preferable.
[0071] With regard to the cyclic molecule having the ring as
described above, a plurality of the cyclic molecules clathrate one
axle molecule. In general, when the maximum clathration number of
the cyclic molecules which can form clathration per one axle
molecule is taken as 1, the clathration number of the cyclic
molecules is in the range preferably from 0.001 to 0.6, further
preferably from 0.002 to 0.5, and still further preferably from
0.003 to 0.4. If the clathration number of the cyclic molecules is
excessively large, the cyclic molecules thickly exist relative to
one axle molecule, and therefore the movability of the cyclic
molecules is reduced and the photochromism tends to be reduced.
Moreover, if the clathration number thereof is excessively small,
the clearance between the axle molecules is narrowed, resulting in
reducing the clearance in which the reversible reaction of the
photochromic compound molecule is allowable, and the photochromism
tends to be reduced as well.
[0072] In addition, the maximum clathration number of the cyclic
molecules relative to one axle molecule can be calculated from a
length of the axle molecule and a thickness of the ring of the
cyclic molecule.
[0073] To take an example of a case where the chain portion of the
axle molecule is formed of polyethylene glycol and the ring of the
cyclic molecule is the .alpha.-cyclodextrin ring, for example, the
maximum clathration number thereof can be calculated as described
below.
[0074] More specifically, an equivalent to two repeating units
[--CH.sub.2--CH.sub.2O-] of the polyethylene glycol is approximated
to a thickness of one .alpha.-cyclodextrin ring. Accordingly, the
number of repeating units is calculated from a molecular weight of
this polyethylene glycol, and one half of this number of repeating
units is determined as the maximum clathration number of the cyclic
molecules. This maximum clathration number is taken as 1.0, and the
clathration number of the cyclic molecules is to be adjusted within
the range described above.
[0075] Moreover, in the polyrotaxane according to Aspect II, the
side chain is a side chain having a group represented by the
following formula (1):
-A (1)
[0076] (where, A is an organic group having 1 to 10 carbon atoms,
and contains at least one hydroxyl group), in which a pKa of a
hydroxyl group of a compound represented by the following formula
(2):
H-A (2)
is 6 or more and less than 14.
[0077] In addition, as a matter of course, H in the formula (2)
described above represents a hydrogen atom.
[0078] As A in the formula (1), an organic group having 1 to 10
carbon atoms, and a group represented by the following formula
(A-1) or (A-2) can be preferably used.
##STR00001##
[0079] (where, R.sup.7 is a group selected from a hydrocarbon group
having 1 to 4 carbon atoms, a halogen atom, a nitro group, an acyl
group, a methylsulfonyl group, a trifluoromethyl group, a cyano
group and a carboxyl group; p is an integer from 0 to 4; and when
the number of R.sup.7 is two or more, R.sup.7 may be a different
group from each other; and R.sup.8 is a trifluoromethyl group or
hydrogen.).
[0080] The group represented by (A-1) is most preferably a group in
which p is 0. Moreover, as the group represented by (A-1), a group
represented by (A-1') is preferable.
[0081] In the polyrotaxane according to Aspect II, the compound
represented by the formula (2) is a compound having a structure
formed by substituting, for hydrogen, the atom in the bonding site
at which the group represented by the formula (1) is bonded with
the side chain, in which the pKa of the compound represented by the
formula (2) is 6 or more and less than 14.
[0082] Moreover, with regard to the side chain having the secondary
or tertiary hydroxyl group in the polyrotaxane according to Aspect
I, the side chain preferably has the secondary or tertiary hydroxyl
group and is preferably formed by repetition of organic chains in
which the number of carbon atoms is within the range from 3 to 20.
As the side chain in the polyrotaxane according to Aspect II, the
side chain preferably has the group represented by -A and is
preferably formed by repetition of the organic chains in which the
number of carbon atoms is within the range from 3 to 20.
[0083] A weight average molecular weight of such a side chain is in
the range from 200 to 10,000, preferably from 250 to 5,000, and
further preferably from 300 to 1,500. More specifically, if the
side chain is excessively small, a function of securing the
clearance in which the reversible reaction of the photochromic
compound molecule is allowable becomes insufficient. If the side
chain is excessively large, compatibility with other monomers, to
be described later, is deteriorated to easily cause the phase
separation. Moreover, it becomes difficult to densely mix the
photochromic compound, to be described later, in the polyrotaxane
and eventually tends to be difficult in sufficiently utilizing the
space to be secured by the polyrotaxane.
[0084] Further, in the polyrotaxane according to Aspect I, the
polyrotaxane may have the primary hydroxyl group in the side chain.
From the viewpoint of the moldability, however, when the total mole
number of the primary, secondary and tertiary hydroxyl groups in
the side chain is taken as 100%, a proportion of the primary
hydroxyl group is preferably 50% or less, further preferably 20% or
less, and most preferably 0%. More specifically, the reason is
that, if the primary hydroxyl group is low in amount, the
reactivity of the polyrotaxane with the iso(thio)cyanate is
reduced, and the moldability is improved.
[0085] The side chain having the secondary or tertiary hydroxyl
group as described above is introduced thereinto by using a
functional group of the ring of the cyclic molecule and modifying
this functional group. For example, the .alpha.-cyclodextrin ring
has eighteen hydroxyl groups as the functional group, and the side
chain is introduced thereinto through this hydroxyl group. More
specifically, a maximum of up to eighteen side chains can be
introduced into one .alpha.-cyclodextrin ring. In the present
invention, in order to sufficiently develop the function of the
side chain described above, 6% or more, and particularly 30% or
more of the total number of functional groups of such a ring is
preferably modified with the side chain. More specifically, 6% or
more and 100% or less of the total number of functional groups are
preferably modified with the side chain, 30% or more and 100% or
less of the total number of functional groups are further
preferably modified with the side chain, and 30% or more and 80% or
less of the total number of functional groups are still further
preferably modified with the side chain. Incidentally, when the
side chains are bonded with nine hydroxyl groups among the eighteen
hydroxyl groups in the .alpha.-cyclodextrin ring, a degree of
modification therewith is deemed to be 50% (namely, 0.5).
[0086] In the polyrotaxane according to Aspect I, as long as the
side chain (the organic chain) as described above has the secondary
or tertiary hydroxyl group, and further a size of the side chain is
within the range described above, the side chain may have the
straight chain or branched chain. The side chain having an
appropriate size can be introduced thereinto by using ring-opening
polymerization; radical polymerization; cationic polymerization;
anionic polymerization; and living radical polymerization such as
atom transfer radical polymerization, RAFT polymerization and NMP
polymerization, and by reacting an appropriate compound with the
functional group of the ring. When the side chain has neither the
secondary hydroxyl group nor the tertiary hydroxyl group upon
introducing the side chain by polymerization, a reaction only needs
to be performed so that the polyrotaxane may have such a structure
at the end of the side chain. Although the details will be
described later, for example, if the hydroxyl group introduced into
the side chain is the primary hydroxyl group, the side chain into
which the secondary or tertiary hydroxyl group is introduced can be
obtained by reacting, with the primary hydroxyl group of the side
chain, the isocyanate compound in which the secondary or tertiary
hydroxyl group is protected, and then deprotecting the resulting
material.
[0087] As a preferred structure of the side chain, the polyrotaxane
most preferably has a side chain represented by the following
formula (1):
##STR00002##
[0088] In the formula (1), Q is formed of at least one kind
selected from structures represented by the following formulas
(Q-1), (Q-2) and (Q-3).
##STR00003##
[0089] (where, G is a straight-chain alkylene group or alkenylene
group having 1 to 8 carbon atoms; a branched-chain alkylene group
or alkenylene group having 3 to 20 carbon atoms; an alkylene group
or alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond, a --NH-- bond, a --SO--
bond or a --SiO-- bond; or an alkylene group formed by replacement
of a part of hydrogen of the alkylene group by at least one kind
selected from the group consisting of a hydroxyl group, a carboxyl
group, an acyl group, a phenyl group, a halogen atom and an olefin
group, and when a plurality of G exist, each G may be a same group
or a different group, and n.sub.1, n.sub.2 and n.sub.3 are each
independently an integer from 1 to 200), and
[0090] when Q is formed of two or more kinds selected from the
formulas (Q-1), (Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may
be a same group or a different group, a total of n.sub.1, n.sub.2
and n.sub.3 is an integer from 1 to 200, and R.sup.1 and R.sup.2
are each independently a group selected from hydrogen, a
straight-chain alkyl group having 1 to 6 carbon atoms or a
branched-chain alkyl group having 1 to 6 carbon atoms, excluding a
group in which R.sup.1 and R.sup.2 are simultaneously hydrogen.
[0091] Moreover, as a preferred structure of the side chain, the
polyrotaxane most preferably has a side chain represented by the
following formula (1') as well:
##STR00004##
[0092] In the formula (1'), Q is formed of at least one kind
selected from structures represented by the following formulas
(Q-1), (Q-2) and (Q-3)
##STR00005##
[0093] (where, G is a straight-chain alkylene group or alkenylene
group having 1 to 8 carbon atoms; a branched-chain alkylene group
or alkenylene group having 3 to 20 carbon atoms; an alkylene group
or alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond, a --NH-- bond, a --SO--
bond or a --SiO-- bond; or an alkylene group formed by replacement
of a part of hydrogen of the alkylene group by at least one kind
selected from the group consisting of a hydroxyl group, a carboxyl
group, an acyl group, a phenyl group, a halogen atom and an olefin
group, and when a plurality of G exist, each G may be a same group
or a different group, and n.sub.1, n.sub.2 and n.sub.3 are each
independently an integer from 1 to 200), and
[0094] when Q is formed of two or more kinds selected from the
formulas (Q-1), (Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may
be a same group or a different group, a total of n.sub.1, n.sub.2
and n.sub.3 is an integer from 1 to 200, X is an alkylene group or
alkenylene group having 2 to 20 carbon atoms, or an alkylene group
or alkenylene formed by replacement of a part of the alkylene group
or alkenylene group by a --O-- bond or a --NH-- bond, and R.sup.3
and R.sup.4 are each independently selected from hydrogen, a
straight-chain alkyl group having 1 to 6 carbon atoms or a
branched-chain alkyl group having 1 to 6 carbon atoms, excluding a
group in which R.sup.3 and R.sup.4 are simultaneously hydrogen; and
R.sup.5 is carbon or sulfur.
[0095] Further, in the polyrotaxane according to Aspect II, the
polyrotaxane may have the hydroxyl group the pKa of which is less
than 6 or 14 or more in the side chain. From the viewpoint of the
moldability, however, when the total mole number of the hydroxyl
groups in the side chain is taken as 100%, a proportion of the
hydroxyl group the pKa of which is less than 6 and 14 or more is
preferably 50% or less, further preferably 20% or less, and most
preferably 0%. More specifically, the reason is that, if the
hydroxyl group the pKa of which is less than 6 and 14 or more is
low in amount, the reactivity with the iso(thio)cyanate can be
easily controlled, the rate of polymerization can be adjusted, and
the moldability or the cloudiness described above can be
suppressed.
[0096] The side chain having the hydroxyl group the pKa of which is
6 or more and less than 14 is introduced thereinto by using the
functional group of the ring of the cyclic molecule and modifying
the functional group. For example, the .alpha.-cyclodextrin ring
has eighteen hydroxyl groups as the functional group, and the side
chain is introduced thereinto through the hydroxyl group. More
specifically, the maximum of up to eighteen side chains can be
introduced into one .alpha.-cyclodextrin ring. In the present
invention, in order to sufficiently develop the function of the
side chain described above, 6% or more, and particularly 30% or
more of the total number of the functional groups of such a ring is
preferably modified with the side ring. More specifically, 6% or
more and 100% or less of the total number of the functional groups
are preferably modified with the side chain, 30% or more and 100%
or less of the total number of functional groups are further
preferably modified with the side chain, and 30% or more and 80% or
less of the total number of the functional groups are still further
preferably modified with the side chain. Incidentally, when the
side chains are bonded with nine hydroxyl groups among the eighteen
hydroxyl groups of the .alpha.-cyclodextrin ring, the degree of
modification therewith is deemed to be 50% (namely, 0.5).
[0097] In the polyrotaxane according to Aspect II, as long as the
side chain (the organic chain) as described above has the hydroxyl
group the pKa of which is 6 or more and less than 14, and further
the size of the side chain is within the range described above, the
side chain may have the straight chain or branched chain. The side
chain having an appropriate size can be introduced thereinto by
using ring-opening polymerization; radical polymerization; cationic
polymerization; anionic polymerization; and living radical
polymerization such as atom transfer radical polymerization, RAFT
polymerization and NMP polymerization, and by reacting an
appropriate compound with the functional group of the ring. When
the side chain has no hydroxyl group the pKa of which is 6 or more
and less than 14 upon introducing the side chain by polymerization,
a reaction only needs to be further performed so that the
polyrotaxane may have a structure in which the hydroxyl group the
pKa of which is 6 or more and less than 14 is introduced into the
side chain. Although the details will be described later, for
example, when the pKa of the hydroxyl group introduced into the
side chain is less than 6 or 14 or more, the side chain into which
the hydroxyl group the pKa of which is 6 or more and less than 14
is introduced can be obtained by reacting, with the hydroxyl group
in the side chain, the compound having the hydroxyl group the pKa
of which is 6 or more and less than 14 or the compound in which the
hydroxyl group the pKa of which is 6 or more and less than 14 is
protected.
[0098] As a preferred structure of the side chain, a side chain
represented by the following formula (3) is most preferably
introduced thereinto.
-Q-A (3)
[0099] In the formula (3), Q is formed of at least one kind
selected from structures represented by the following formulas
(Q-1), (Q-2) and (Q-3).
##STR00006##
[0100] (where, G is a straight-chain alkylene group or alkenylene
group having 1 to 8 carbon atoms; a branched-chain alkylene group
or alkenylene group having 3 to 20 carbon atoms; an alkylene group
or alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond, a --NH-- bond, a --SO--
bond or a --SiO-- bond; or an alkylene group formed by replacement
of a part of hydrogen of the alkylene group by at least one kind
selected from the group consisting of a carboxyl group, an acyl
group, a phenyl group, a halogen atom and an olefin group, and when
a plurality of G exist, each G may be a same group or a different
group, and n.sub.1, n.sub.2 and n.sub.3 are each independently an
integer from 1 to 200), and
[0101] when Q is formed of two or more kinds selected from the
formulas (Q-1), (Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may
be a same group or a different group, a total of n.sub.1, n.sub.2
and n.sub.3 is an integer from 1 to 200, and A is an organic group
having 1 to 10 carbon atoms and contains at least one hydroxyl
group. In addition, the pKa of the hydroxyl group of the compound
represented by H-A is 6 or more and less than 14.
[0102] As a preferred structure of the side chain, a side chain
represented by the following formula (3') is most preferably
introduced thereinto.
##STR00007##
[0103] In the formula (3'), Q is formed of at least one kind
selected from structures represented by the following formulas
(Q-1), (Q-2) and (Q-3).
##STR00008##
[0104] (where, G is a straight-chain alkylene group or alkenylene
group having 1 to 8 carbon atoms; a branched-chain alkylene group
or alkenylene group having 3 to 20 carbon atoms; an alkylene group
or alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond, a --NH-- bond, a --SO--
bond or a --SiO-- bond; or an alkylene group formed by replacement
of a part of hydrogen of the alkylene group by at least one kind
selected from the group consisting of a carboxyl group, an acyl
group, a phenyl group, a halogen atom and an olefin group, and when
a plurality of G exist, each G may be a same group or a different
group, and n.sub.1, n.sub.2 and n.sub.3 are each independently an
integer from 1 to 200), and
[0105] when Q is formed of two or more kinds selected from the
formulas (Q-1), (Q-2) and (Q-3), G constituting (Q-1) to (Q-3) may
be a same group or a different group, a total of n.sub.1, n.sub.2
and n.sub.3 is an integer from 1 to 200, and R.sup.6 is carbon or
sulfur, X is an alkylene group or alkenylene group having 2 to 20
carbon atoms; or an alkylene group or alkenylene group formed by
replacement of a part of the alkylene group or alkenylene group by
a --O-- bond, or a --NH-- bond, and A is an organic group having 1
to 10 carbon atoms and contains at least one hydroxyl group.
[0106] In the preferred structure of the side chain represented by
the formula (1), Q has either a structure represented by the
formula (Q-1) or a structure represented by the formula (Q-2) or
both the structures, and n.sub.1 and n.sub.2 are each independently
in the range from 1 to 100, and in the range from 1 to 100 in
total, further preferably, Q has either a structure represented by
the formula (Q-1) or a structure represented by the formula (Q-2)
or both the structures, and n.sub.1 and n.sub.2 are each
independently in the range from 1 to 75, and in the range from 1 to
75 in total, and most preferably, Q has a structure represented by
the formula (Q-1), and n.sub.1 is in the range from 1 to 50.
[0107] In the polyrotaxane according to Aspect I, as the method for
introducing the side chain having the secondary or tertiary
hydroxyl group thereinto as described above, the side chain is
preferably introduced thereinto by the ring-opening polymerization,
and as the ring-opening polymerization, the side chain derived from
the cyclic compound such as the cyclic ether, cyclic siloxane,
cyclic lactone, cyclic lactam, cyclic acetal, cyclic amine or
cyclic carbonate can be introduced thereinto. When the end is the
primary hydroxyl group upon being introduced thereinto, the primary
hydroxyl group only needs to be changed to the secondary or
tertiary hydroxyl group according to the technique as described
above.
[0108] Among these compounds, from viewpoints of ease of
availability, high reactivity, and ease of adjustment of the size
(molecular weight), cyclic ether, cyclic lactone, cyclic lactam, or
cyclic carbonate is preferably used. If the ring-opening
polymerization is performed by using such a compound, the hydroxyl
group can be introduced into the end, but a category of the
hydroxyl group at the end is determined by a structure of the
compound used. When the hydroxyl group of the side chain introduced
thereinto is the primary hydroxyl group, the secondary or tertiary
hydroxyl group may be introduced thereinto according to the
technique described above. Specific examples of the cyclic ether,
the cyclic lactone, the cyclic lactam and the cyclic carbonate
which may be the side chain are described below.
[0109] Cyclic ether from which the primary hydroxyl group may be
introduced into the side chain by the ring-opening
polymerization:
[0110] ethylene oxide, 1,2-propylene oxide and oxetane.
[0111] Cyclic ether from which the secondary or tertiary hydroxyl
group may be introduced into the side chain by the ring-opening
polymerization:
[0112] epichlorohydrin, epibromohydrin, 1,2-butylene oxide,
2,3-butylene oxide and isobutylene oxide.
[0113] Cyclic lactone from which the primary hydroxyl group may be
introduced into the side chain by the ring-opening
polymerization:
[0114] .beta.-propiolactone, .gamma.-butyrolactone,
.alpha.-hexyl-.gamma.-butyrolactone,
.alpha.-heptyl-.gamma.-butyrolactone,
.alpha.-hydroxy-.gamma.-butyrolactone,
.alpha.-methylene-.gamma.-butyrolactone,
.alpha.,.alpha.-dimethyl-.gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone, .gamma.-nonanolactone,
.gamma.-undecanolactone, .gamma.-valerolactone,
.alpha.-bromo-.gamma.-butyrolactone, .gamma.-crotonolactone,
.alpha.-methylene-.gamma.-butyrolactone,
.alpha.-methacryloyloxy-.gamma.-butyrolactone,
.beta.-methacryloyloxy-.gamma.-butyrolactone,
.delta.-valerolactone, .alpha.-methyl-.delta.-valerolactone,
.alpha.-ethyl-.delta.-valerolactone,
.alpha.-hexyl-.delta.-valerolactone, 1,4-dioxan-2-one,
1,5-dioxepan-2-one, .epsilon.-caprolactone,
.alpha.-methyl-.epsilon.-caprolactone,
.alpha.-ethyl-.epsilon.-caprolactone,
.alpha.-hexyl-.epsilon.-caprolactone,
5-n-propyl-.epsilon.-caprolactone, 5-n-hexyl-.epsilon.-caprolactone
and .zeta.-enantholactone.
[0115] Cyclic lactone from the secondary or tertiary hydroxyl group
may be introduced into the side chain by the ring-opening
polymerization:
[0116] .beta.-methylpropiolactone, .gamma.-hexanolactone,
.gamma.-heptanolactone, .gamma.-octanolactone,
.gamma.-decanolactone, .gamma.-dodecanolactone,
.gamma.-methyl-.gamma.-decanolactone, DL-pantolactone,
.delta.-hexanolactone, .delta.-octanolactone,
.delta.-nonanolactone, .delta.-decanolactone,
.delta.-undecanolactone, .delta.-dodecanolactone,
.delta.-tridecanolactone, .delta.-tetradecanolactone,
.alpha.,.epsilon.-dimethyl-.epsilon.-caprolactone and
7.alpha.-nonyloxepan-2-one.
[0117] Cyclic lactam from which the primary hydroxyl group may be
introduced into the side chain by the ring-opening
polymerization:
[0118] .epsilon.-caprolactam, .gamma.-butyrolactam and
DL-.alpha.-amino-.epsilon.-caprolactam.
[0119] Cyclic carbonate from which the primary hydroxyl group may
be introduced into the side chain by the ring-opening
polymerization:
[0120] ethylene carbonate and vinylene carbonate.
[0121] Cyclic carbonate from which the secondary hydroxyl group may
be introduced into the side chain by the ring-opening
polymerization:
[0122] propylene carbonate and 1,2-butylene carbonate.
[0123] The cyclic compounds described above can be used not only
alone but also in combination with a plurality of kinds.
[0124] In the polyrotaxane according to Aspect I, a compound
further preferably used for the ring-opening polymerization is
cyclic lactone and cyclic lactam. Among these compounds, a compound
preferably used is lactone such as .epsilon.-caprolactone,
.alpha.-acetyl-.gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone, .gamma.-butyrolactone,
.gamma.-valerolactone, .epsilon.-caprolactam and
.gamma.-butyrolactam. In view of simplicity of synthesis and ease
of control of the molecular weight, the side chain is most
preferably .epsilon.-caprolactone or .epsilon.-caprolactam. In
addition, if the side chain is introduced thereinto by using
.gamma.-valerolactone in the compounds, the polyrotaxane having the
side chain in which the secondary hydroxyl group is introduced into
the end of the side chain can be obtained. When a group introduced
thereinto after the ring-opening polymerization is the primary
hydroxyl group, also as described above, for example, the secondary
or tertiary hydroxyl group only needs to be introduced thereinto by
reacting the primary hydroxyl group with the isocyanate compound in
which the secondary or tertiary hydroxyl group is protected, and
then deprotecting the resulting material.
[0125] In the polyrotaxane according to Aspect II, as the method
for introducing the side chain having the hydroxyl group the pKa of
which is 6 or more and less than 14 as described above, the side
chain is preferably introduced thereinto by the ring-opening
polymerization, and as the ring-opening polymerization, the side
chain derived from the cyclic compound of cyclic ether, cyclic
siloxane, cyclic lactone, cyclic lactam, cyclic acetal, cyclic
amine and cyclic carbonate can be introduced thereinto.
[0126] Among these compounds, from the viewpoints of ease of
availability, high reactivity and further ease of adjustment of the
size (molecular weight), cyclic ether, cyclic lactone, cyclic
lactam or cyclic carbonate is preferably used. If the ring-opening
polymerization is performed by using such a compound, the hydroxyl
group can be introduced into the end, but the pKa of the hydroxyl
group at the end is determined by the structure of the compound
used. When the pKa of the hydroxyl group of the side chain
introduced thereinto is less than 6 or 14 or more, the hydroxyl
group the pKa of which is 6 or more and less than 14 only needs to
be introduced thereinto according to the technique described above.
Specific examples of the cyclic ether, the cyclic lactone, the
cyclic lactam and the cyclic carbonate which may be the side chain
are described below.
[0127] Cyclic Ether:
[0128] ethylene oxide, 1,2-propylene oxide, oxetane,
epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene
oxide and isobutylene oxide.
[0129] Cyclic Lactone:
[0130] .beta.-propiolactone, .gamma.-butyrolactone,
.alpha.-hexyl-.gamma.-butyrolactone,
.alpha.-heptyl-.gamma.-butyrolactone,
.alpha.-hydroxy-.gamma.-butyrolactone,
.alpha.-methylene-.gamma.-butyrolactone,
.alpha.,.alpha.-dimethyl-.gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone, .gamma.-nonanolactone,
.gamma.-undecanolactone, .gamma.-valerolactone,
.alpha.-bromo-.gamma.-butyrolactone, .gamma.-crotonolactone,
.alpha.-methylene-.gamma.-butyrolactone,
.alpha.-methacryloyloxy-.gamma.-butyrolactone,
.beta.-methacryloyloxy-.gamma.-butyrolactone,
.delta.-valerolactone, .alpha.-methyl-.delta.-valerolactone,
.alpha.-ethyl-.delta.-valerolactone,
.alpha.-hexyl-.delta.-valerolactone, 1,4-dioxan-2-one,
1,5-dioxepan-2-one, .epsilon.-caprolactone,
.alpha.-methyl-.epsilon.-caprolactone,
.alpha.-ethyl-.epsilon.-caprolactone,
.alpha.-hexyl-.epsilon.-caprolactone,
5-n-propyl-.epsilon.-caprolactone,
5-n-hexyl-.epsilon.-caprolactone, .zeta.-enantholactone,
.beta.-methylpropiolactone, .gamma.-hexanolactone,
.gamma.-heptanolactone, .gamma.-octanolactone,
.gamma.-decanolactone, .gamma.-dodecanolactone,
.gamma.-methyl-.gamma.-decanolactone, DL-pantolactone,
.delta.-hexanolactone, .delta.-octanolactone,
.delta.-nonanolactone, .delta.-decanolactone,
.delta.-undecanolactone, .delta.-dodecanolactone,
.delta.-tridecanolactone, .delta.-tetradecanolactone,
.alpha.,.epsilon.-dimethyl-.epsilon.-caprolactone and
7.alpha.-nonyloxepan-2-one.
[0131] Cyclic lactam: .epsilon.-caprolactam, .gamma.-butyrolactam
and DL-.alpha.-amino-.epsilon.-caprolactam.
[0132] Cyclic carbonate: ethylene carbonate, vinylene carbonate,
propylene carbonate and 1,2-butylene carbonate.
[0133] The cyclic compounds described above can be used not only
alone but also in combination with a plurality of kinds.
[0134] In the polyrotaxane according to Aspect II, a compound
further preferably used for the ring-opening polymerization is
cyclic lactone and cyclic lactam. Among these compounds, a compound
preferably used is lactone such as .epsilon.-caprolactone,
.alpha.-acetyl-.gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone, .gamma.-butyrolactone,
.gamma.-valerolactone, .epsilon.-caprolactam and
.gamma.-butyrolactam. In view of simplicity of synthesis and ease
of control of the molecular weight, the side chain is most
preferably .epsilon.-caprolactone or .epsilon.-caprolactam. When
the hydroxyl group the pKa of which is less than 6 or 14 or more is
introduced thereinto after polymerization in the side chain, also
as described above, for example, the hydroxyl group the pKa of
which is 6 or more and less than 14 only needs to be introduced
thereinto by reacting the hydroxyl group with the isocyanate
compound in which the hydroxyl group the pKa of which is 6 or more
and less than 14 is protected, and then deprotecting the resulting
material.
[0135] Thus, when the side chain is introduced thereinto by
reacting the cyclic compound therewith by the ring-opening
polymerization, the functional group (for example, the hydroxyl
group) bound to the ring has poor reactivity, and has difficulty in
directly reacting a large molecule therewith particularly by steric
hindrance or the like in several cases. In such a case, for
example, the production method can employ a means in which, in
order to react caprolactone or the like therewith, the functional
group (hydroxyl group) enriched with reactivity is introduced
thereinto by performing hydroxypropylation by reacting a low
molecular-weight compound such as propylene oxide with the
functional group, and then the side chain is introduced thereinto
by the ring-opening reaction using the cyclic compound described
above.
[0136] Further, as the production method for the polyrotaxane being
characterized in that the side chain having the secondary or
tertiary hydroxyl group is introduced into at least part of the
cyclic molecule (polyrotaxane according to Aspect I) according to
the present invention, in view of simplicity of synthesis and ease
of control of the molecular weight, the production method
preferably includes reacting, with a compound represented by the
following formula (2), a polyrotaxane having a composite molecular
structure formed of an axle molecule and a plurality of cyclic
molecules clathrating the axle molecule, and the polyrotaxane in
which a side chain having a primary hydroxyl group is introduced
into at least part of the cyclic molecule of the polyrotaxane.
Moreover, the production method most preferably includes reacting,
with the compound represented by the following formula (2), the
polyrotaxane in which the side chain having the primary hydroxyl
group is introduced into at least part of the cyclic molecule of
the polyrotaxane, and then deprotecting Z.
##STR00009##
[0137] (where, X is an alkylene group or alkenylene group having 2
to 20 carbon atoms, or an alkylene group or alkenylene group formed
by replacement of a part of the alkylene group or alkenylene group
by a --O-- bond or a --NH-- bond; Z is a group selected from the
group consisting of the following formulas Z-1 to Z-9; R.sup.3 and
R.sup.4 are each independently selected from hydrogen, a
straight-chain alkyl group having 1 to 6 carbon atoms or a
branched-chain alkyl group having 1 to 6 carbon atoms, excluding a
group in which R.sup.3 and R.sup.4 are simultaneously hydrogen; and
R.sup.5 is carbon or sulfur.)
##STR00010##
[0138] The alkylene group may be a branched-chain alkylene group or
straight-chain alkylene group. Moreover, the alkenylene group may
be a branched-chain alkenylene group or straight-chain alkenylene
group.
[0139] Specific examples of the compound represented by the formula
(2) include: 2-methyl-2-(trimethylsiloxy)propyl isocyanate,
2-methyl-2-(t-butyldimethylsiloxy)propyl isocyanate,
2-(trimethylsiloxy)propyl isocyanate,
2-(t-butyldimethylsiloxy)propyl isocyanate,
[(2-isocyanato-1,1-dimethylethoxy)methyl]benzene and
(2-isocyanato-1-methylpropoxy)benzene, and particularly preferably
include: 2-methyl-2-(trimethylsiloxy)propyl isocyanate and
2-methyl-2-(t-butyldimethylsiloxy)propyl isocyanate.
[0140] As the production method including reacting, with the
compound represented by the following formula (2), the polyrotaxane
in which the side chain having the primary hydroxyl group is
introduced into at least part of the cyclic molecule, and then
deprotecting Z, the following method can be employed.
[0141] The polyrotaxane in which the side chain having the tertiary
hydroxyl group is introduced into at least part of the cyclic
molecule can be obtained by preparing the polyrotaxane having the
primary hydroxyl group in the side chain, according to the method
described in Patent literature 8, and introducing
2-methy-2-(trimethylsiloxy)propyl isocyanate into the primary
hydroxyl group of the polyrotaxane, and then deprotecting the
resulting material by using tetra-n-butylammonium fluoride (TBAF).
When the secondary hydroxyl group is introduced thereinto according
to the production method described above, 2-(trimethylsiloxy)propyl
isocyanate or 2-(t-butyldimethylsiloxy) propyl isocyanate only
needs to be used in place of 2-methyl-2-(trimethylsiloxy)propyl
isocyanate.
[0142] In the polyrotaxane according to Aspect I, as the
polyrotaxane most preferably used, a polyrotaxane in which
polyethylene glycol having adamantyl groups bound at both ends is
applied as an axle molecule, and a cyclic molecule having an
.alpha.-cyclodextrin ring is applied as a ring, and a side chain is
further introduced into the ring by .epsilon.-polycaprolactone, and
a secondary or tertiary hydroxyl group is introduced into an end
according to the production method described above is preferably
used.
[0143] Further, as the production method for the polyrotaxane being
characterized in that the side chain having the hydroxyl group the
pKa of which is 6 or more and less than 14 is introduced into at
least part of the cyclic molecule (polyrotaxane according to Aspect
II) according to the present invention, in view of simplicity of
synthesis and ease of control of the molecular weight, the
production method preferably includes reacting, with a compound
represented by the following formula (4), a polyrotaxane having a
composite molecular structure formed of an axle molecule and a
plurality of cyclic molecules clathrating the axle molecule, and
the polyrotaxane in which a side chain having a primary hydroxyl
group a pKa of which is 14 or more is introduced into at least part
of the cyclic molecule of the polyrotaxane. Moreover, the
production method most preferably includes reacting, with the
compound represented by the following formula (4), the polyrotaxane
in which the side chain having the primary hydroxyl group the pKa
of which is 14 or more is introduced into at least part of the
cyclic molecule of the polyrotaxane, and then deprotecting Z.
[Formula 11]
O.dbd.R.sup.6.dbd.N--X-T-O--Z (4)
[0144] [where, R.sup.6 is carbon or sulfur, X is an alkylene group
or alkenylene group having 2 to 20 carbons, or an alkylene group or
alkenylene group formed by replacement of a part of the alkylene
group or alkenylene group by a --O-- bond or a --NH-- bond, where,
T is a group selected from the group consisting of the following
formulas (T-1) or (T-2):
##STR00011##
[0145] (where, R.sup.7 is a group selected from a hydrocarbon group
having 1 to 4 carbon atoms, a halogen atom, a nitro group, an acyl
group, a methylsulfonyl group, a trifluoromethyl group, a cyano
group and a carboxyl group; p is an integer from 0 to 4; and when
the number of R.sup.7 is two or more, R.sup.7 may be a different
group from each other, R.sup.8 is a trifluoromethyl group or
hydrogen), and where, Z is a group selected from the group
consisting of the following formulas Z-1 to Z-9]:
##STR00012##
[0146] The group represented by (T-1) is most preferably a group in
which p is 0.
[0147] The alkylene group may be a branched-chain alkylene group or
straight-chain alkylene group. Moreover, the alkenylene group may
be a branched-chain alkenylene group or straight-chain alkenylene
group.
[0148] Specific examples of the compound represented by the formula
(4) include: 1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene,
1-(2-isothiocyanateethyl)-4-[(trimethylsilyl)oxy]-benzene,
1-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-4-(2-isocyanatepropyl)benzene,
1-(2-isocyanatoethyl)-4-methoxybenzene,
1-(2-isocyanatoethyl)-4-(phenylmethoxy)-benzene,
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propane
isocyanate, 4,4,4-trifluoro-3-(phenylmethoxy)-1-butane isocyanate
and 4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butane
isocyanate. In addition,
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propane
isocyanate, 4,4,4-trifluoro-3-(phenylmethoxy)-1-butane isocyanate
or 4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butane isocyanate
can be obtained by converting a primary amine group into an
isocyanate group by reacting, with phosgene, the primary amine
group of
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine,
4,4,4-trifluoro-3-(phenylmethoxy)-1-butaneamine or
4,4,4-trifluoro-3-[(4-methoxyphenyl)methoxy]-1-butaneamine.
[0149] As the production method including reacting, with the
compound represented by the formula (4), the polyrotaxane in which
the side chain having the primary hydroxyl group the pKa of which
is 14 or more is introduced into at least part of the cyclic
molecule, and then deprotecting Z, the method as described below
can be employed.
[0150] The polyrotaxane in which the side chain having the hydroxyl
group the pKa of which is 6 or more and less than 14 is introduced
into at least part of the cyclic molecule can be obtained by
preparing the polyrotaxane having the hydroxyl group the pKa of
which is 14 or more in the side chain, according to the method
described in Patent literature 8, and introducing
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene into the
primary hydroxyl group the pKa of which is 14 or more in the
polyrotaxane, and then deprotecting the resulting material by using
tetra-n-butylammonium fluoride (TBAF).
[0151] In the polyrotaxane according to Aspect II, as the
polyrotaxane most preferably used, a polyrotaxane in which
polyethylene glycol having adamantyl groups bound at both ends is
applied as an axle molecule, and a cyclic molecule having an
.alpha.-cyclodextrin ring is applied as a ring, and a side chain is
further introduced into the ring by .epsilon.-polycaprolactone, and
a hydroxyl group a pKa of which is 6 or more and less than 14 is
introduced into an end according to the production method described
above is preferably used.
[0152] The polyrotaxane (A) according to the present invention (for
example, the polyrotaxane according to Aspect I or Aspect II) can
be used as an optical composition. For example, when the
polyrotaxane (A) is used together with a (B) component to be
described later to form the optical composition, the optical
composition can be preferably used for a plastic lens such as an
eyeglass lens.
[0153] Next, (B) will be described.
[0154] <(B) Compound Having Two or More Groups of at Least One
Kind Selected from an Isocyanate Group and an Isothiocyanate Group
in One Molecule>
[0155] A compound having two or more groups of at least one kind
selected from an isocyanate group and an isothiocyanate group in
one molecule (hereinafter, also referred to simply as
"polyiso(thio)cyanate compound") that forms the optical composition
according to the present invention is a compound having two or more
groups (in total) of an isocyanate group and an isothiocyanate
group in one molecule of the polyiso(thio)cyanate compound. Among
the polyiso(thio)cyanate compounds, specific examples of the
polyisocyanate compound include: aliphatic isocyanate, alicyclic
isocyanate, aromatic isocyanate, sulfur-containing aliphatic
isocyanate, aliphatic sulfide-based isocyanate, aromatic
sulfide-based isocyanate, aliphatic sulfone-based isocyanate,
aromatic sulfone-based isocyanate, sulfonate-based isocyanate,
aromatic sulfonic acid amide-based isocyanate and sulfur-containing
heterocyclic ring isocyanate.
[0156] Moreover, specific examples of the polyisothiocyanate
compound include: aliphatic isothiocyanate, alicyclic
isothiocyanate, aromatic isothiocyanate, heterocyclic
ring-containing isothiocyanate, carbonyl isothiocyanate,
sulfur-containing aliphatic isothiocyanate, sulfur-containing
aromatic isothiocyanate and sulfur-containing heterocyclic ring
isothiocyanate. Specific examples of these polyiso (thio)cyanate
compounds can include the compounds described below.
[0157] Aliphatic isocyanate; ethylene diisocyanate, trimethylene
diisocyanate, tetramethylene diisocyanate, hexamethylene
diisocyanate, octamethylene diisocyanate, nonamethylene
diisocyanate, 2,2'-dimethylpentane diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate, decamethylene
diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate,
1,6,11-trimethylundecamethylene diisocyanate,
1,3,6-trimethylhexamethylene diisocyanate,
1,8-diisocyanato-4-isocyanatomethyloctane,
2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane,
bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether,
1,4-butylene glycol dipropyl ether-.omega.,.omega.'-diisocyanate,
lysine diisocyanatomethyl ester, lysine triisocyanate,
2-isocyanatoethyl-2,6-diisocyanate hexanoate and
2-isocyanatopropyl-2,6-diisocyanate hexanoate.
[0158] Alicyclic isocyanate: isophorone diisocyanate,
(bicyclo[2.2.1]heptane-2,5-diyl)bismethylene diisocyanate,
(bicyclo[2.2.1]heptane-2,6-diyl)bismethylene diisocyanate,
2.beta.,5.alpha.-bis(isocyanato)norbornane,
2.beta.,5.beta.-bis(isocyanato)norbornane,
2.beta.,6.alpha.-bis(isocyanato)norbornane,
2.beta.,6.beta.-bis(isocyanato)norbornane,
2,6-di(isocyanatomethyl)furan, bis(isocyanatomethyl)cyclohexane,
dicyclohexylmethane diisocyanate, 4,4-isopropylidene
bis(cyclohexylisocyanate), cyclohexane diisocyanate,
methylcyclohexane diisocyanate, dicyclohexyldimethylmethane
diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate,
bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid
diisocyanate,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,-
1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,-
1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,-
1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,-
1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2-
,2,1]-heptane,
2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2-
,2,1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2-
,2,1]-heptane,
2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2-
,2,1]-heptane, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,
2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,
1,3,5-tris(isocyanatomethyl)cyclohexane,
3,8-bis(isocyanatomethyl)tricyclodecane,
3,9-bis(isocyanatomethyl)tricyclodecane,
4,8-bis(isocyanatomethyl)tricyclodecane,
4,9-bis(isocyanatomethyl)tricyclodecane, 1,5-diisocyanatodecalin,
2,7-diisocyanatodecalin, 1,4-diisocyanatodecalin,
2,6-diisocyanatodecalin, a mixture of
bicyclo[4.3.0]nonane-3,7-diisocyanate and
bicyclo[4.3.0]nonane-4,8-diisocyanate, a mixture of
bicycle[2.2.1]heptane-2,5-diisocyanate and
bicyclo[2.2.1]heptane-2,6-diisocyanate, a mixture of
bicycle[2.2.2]octane-2,5-diisocyanate and
bicyclo[2.2.2]octane-2,6-diisocyanate and a mixture of
tricycle[5.2.1.0.sup.2.6]decane-3,8-diisocyanate and
tricyclo[5.2.1.0.sup.2.6]decane-4,9-diisocyanate.
[0159] Aromatic isocyanate: xylylene diisocyanate (o-, m-, p-),
tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene
diisocyanate, 4,5-dichloro-m-xylylene diisocyanate,
2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene
diisocyanate, 4-ethyl-m-xylylene diisocyanate,
bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,
1,3-bis(.alpha.,.alpha.-dimethylisocyanatomethyl)benzene,
1,4-bis(.alpha.,.alpha.-dimethylisocyanatomethyl)benzene,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethylxylylene diisocyanate,
bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene,
bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate,
mesitylene triisocyanate, 2,6-di (isocyanatomethyl) furan,
phenylene diisocyanate, tolylene diisocyanate, ethylphenylene
diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene
diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene
diisocyanate, trimethylbenzene triisocyanate, benzene
triisocyanate, 1,3,5-triisocyanatomethylbenzene, naphthalene
diisocyanate, methylnaphthalene diisocyanate, biphenyl
diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane
diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate,
bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene,
3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane
triisocyanate, polymeric MDI, naphthalene triisocyanate,
diphenylmethane-2,4,4'-triisocyanate,
3-methyldiphenylmethane-4,4',6-triisocyanate,
4-methyl-diphenylmethane-2,3,4',5,6-pentaisocyanate,
phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl
isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene
diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl
ether diisocyanate, ethylene glycol diphenyl ether diisocyanate,
1,3-propylene glycol diphenyl ether diisocyanate, benzophenone
diisocyanate, diethylene glycol diphenyl ether diisocyanate,
dibenzofuran diisocyanate, carbazole diisocyanate, ethylcarbazole
diisocyanate and dichlorocarbazole diisocyanate.
[0160] Sulfur-containing aliphatic isocyanate: thiodiethyl
diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate,
dimethylsulfone diisocyanate, dithiodimethyl diisocyanate,
dithiodiethyl diisocyanate,
1-isocyanatomethylthio-2,3-bis(2-isocyanatoethylthio)propane,
1,2-bis(2-isocyanatoethylthio)ethane,
1,1,2,2-tetrakis(isocyanatomethylthio)ethane,
2,2,5,5-tetrakis(isocyanatomethylthio)-1,4-dithiane,
2,4-dithiapentane-1,3-diisocyanate,
2,4,6-trithiaheptane-3,5-diisocyanate,
2,4,7,9-tetrathiapentane-5,6-diisocyanate,
bis(isocyanatomethylthio)phenylmethane,
bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,
bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane and
1,5-isocyanato-2-isocyanatomethyl-3-thiapentane.
[0161] Aliphatic sulfide-based isocyanate:
bis[2-(isocyanatomethylthio)ethyl]sulfide,
dicyclohexylsulfide-4,4'-diisocyanate,
bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide,
bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide,
bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide and
bis(isocyanatopropyl)disulfide.
[0162] Aromatic sulfide-based isocyanate:
diphenylsulfide-2,4'-diisocyanate,
diphenylsulfide-4,4'-diisocyanate,
3,3'-dimethoxy-4,4'-diisocyanatodibenzyl thioether,
bis(4-isocyanatomethylbenzene)sulfide,
4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate,
diphenyldisulfide-4,4'-diisocyanate,
2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate,
4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate and
4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate.
[0163] Aliphatic sulfone-based isocyanate:
bis(isocyanatomethyl)sulfone.
[0164] Aromatic sulfone-based isocyanate:
diphenylsulfone-4,4'-diisocyanate,
diphenylsulfone-3,3'-diisocyanate,
benzylidenesulfone-4,4'-diisocyanate,
diphenylmethanesulfone-4,4'-diisocyanate,
4-methyldiphenylmethanesulfone-2,4'-diisocyanate,
4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate,
3,3'-dimethoxy-4,4'-diisocyanatodibenzyl sulfone,
4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate,
4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisocyanate and
4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate.
[0165] Sulfonate-based isocyanate:
4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester and
4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol
ester.
[0166] Aromatic sulfonic acid amide-based isocyanate:
4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate,
dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate,
4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate and
4-methyl-3-isocyanatobenzensulfonylanilide-4-methyl-3'-isocyanate.
[0167] Sulfur-containing heterocyclic ring isocyanate:
thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatomethyl,
1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatomethyl,
1,3-dithiolane-4,5-diisocyanate,
1,3-dithiolane-4,5-diisocyanatomethyl,
1,3-dithiolane-2-methyl-4,5-diisocyanatomethyl,
1,3-dithiolane-2,2-diisocyanatoethyl,
tetrahydrothiophene-2,5-diisocyanate,
tetrahydrothiophene-2,5-diisocyanatomethyl,
tetrahydrothiophene-2,5-diisocyanatoethyl,
tetrahydrothiophene-3,4-diisocyanatomethyl, tricyclothiaoctane
diisocyanate, 2-(1,1-diisocyanatomethyl)thiophene,
3-(1,1-diisocyanatomethyl)thiophene,
2-(2-thienylthio)-1,2-diisocyanatopropane,
2-(3-thienylthio)-1,2-diisocyanatopropane,
3-(2-thienyl)-1,5-diisocyanato-2,4-dithiapentane,
3-(3-thienyl)-1,5-diisocyanato-2,4-dithiapentane,
3-(2-thienylthio)-1,5-diisocyanato-2,4-dithiapentane,
3-(3-thienylthio)-1,5-diisocyanato-2,4-dithiapentane,
3-(2-thienylthiomethyl)-1,5-diisocyanato-2,4-dithiapentane,
3-(3-thienylthiomethyl)-1,5-diisocyanato-2,4-dithiapentane,
2,5-(diisocyanatomethyl)thiophene,
2,3-(diisocyanatomethyl)thiophene,
2,4-(diisocyanatomethyl)thiophene,
3,4-(diisocyanatomethyl)thiophene,
2,5-(diisocyanatomethylthio)thiophene,
2,3-(diisocyanatomethylthio)thiophene,
2,4-(diisocyanatomethylthio)thiophene,
3,4-(diisocyanatomethylthio)thiophene and
2,4-bisisocyanatomethyl-1,3,5-trithiane.
[0168] Further, a halogen-substituted product of the
polyisocyanate, an alkyl-substituted product thereof, an
alkoxy-substituted product thereof or a nitro-substituted product
thereof; a prepolymer-type modified product with polyhydric
alcohol; a carbodiimide-modified product therewith; a urea-modified
product therewith; a biuret-modified product therewith; and a
dimerized or trimerized reaction product or the like can also be
used.
[0169] Aliphatic isothiocyanate: 1,2-diisothiocyanatoethane,
1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane,
1,6-diisothiocyanatohexane and p-phenylenediisopropylidene
diisothiocyanate.
[0170] Alicyclic isothiocyanate: cyclohexyl isothiocyanate,
cyclohexane diisothiocyanate,
2,4-bis(isothiocyanatomethyl)norbornane,
2,5-bis(isothiocyanatomethyl)norbornane,
3,4-bis(isothiocyanatomethyl)norbornane and
3,5-bis(isothiocyanatomethyl)norbornane.
[0171] Aromatic isothiocyanate: phenyl isothiocyanate,
1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene,
1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene,
2,5-diisothiocyanato-m-xylene diisocyanate,
4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylene
bis(4-isothiocyanatobenzene), 1,1'-methylene
bis(4-isothiocyanato-2-methylbenzene), 1,1'-methylene
bis(4-isothiocyanato-3-methylbenzene), 1,1'-(1,2-ethanediyl)
bis(4-isothiocyanatobenzene), 4,4'-diisothiocyanato benzophenone,
4,4'-diisothiocyanato-3,3'-dimethyl benzophenone,
benzanilide-3,4'-diisothiocyanate,
diphenylether-4,4'-diisothiocyanate and
diphenylamine-4,4'-diisothiocyanate.
[0172] Heterocyclic ring-containing isothiocyanate:
2,4,6-triisothiocyanato-1,3,5-triazine.
[0173] Carbonyl isothiocyanate: hexanediol diisothiocyanate,
nonanediol diisothiocyanate, carbonic diisothiocyanate,
1,3-benzenedicarbonyl diisothiocyanate, 1-4-benzenedicarbonyl
diisothiocyanate and (2,2-bipyridine)-4,4'-dicarbonyl
diisothiocyanate.
[0174] Further, polyfunctional isothiocyanate having at least one
sulfur atom in addition to a sulfur atom of the isothiocyanate
group can also be used. Specific examples of such polyfunctional
isothiocyanate can include the compounds described below.
[0175] Sulfur-containing aliphatic isothiocyanate:
thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane)
and dithiobis(2-isothiocyanatoethane).
[0176] Sulfur-containing aromatic isothiocyanate:
1-isothiocyanato-4-{(2-isothiocyanato)sulfonyl}benzene,
thiobis(4-isothiocyanatobenzene),
sulfonylbis(4-isothiocyanatobenzene),
sulfinylbis(4-isothiocyanatobenzene),
dithiobis(4-isothiocyanatobenzene),
4-isothiocyanato-1-{(4-isothiocyanatophenyl)sulfonyl}-2-methoxy-benzene,
4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isothiocyanatophenyl
ester and
4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothioc-
yanate.
[0177] Sulfur-containing heterocyclic isothiocyanate:
thiophene-2,5-diisothiocyanate and
1,4-dithiane-2,5-diisothiocyanate.
Preferred Examples for (B) Component
[0178] Preferred examples of the polyiso(thio)cyanate compound
being the (B) component are preferably selected from pentamethylene
diisocyanate, hexamethylene diisocyanate, heptamethylene
diisocyanate, octamethylene diisocyanate, isophorone diisocyanate,
norbornane diisocyanate,
2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,
2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane,
1,2-bis(2-isocyanatoethylthio)ethane, xylene diisocyanate (o-, m-,
p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and
4,4'-diphenylmethane diisocyanate, and may be selected from a
mixture thereof.
Preferred Blending Proportion of (A) and (B) Components
[0179] Further, according to the present invention, with regard to
an optimum blending proportion of the (A) and (B) components
described above for obtaining excellent moldability, mechanical
strength and hardness in the optical article or excellent
photochromic characteristics upon adding the photochromic compound
thereto, to be described later, the resulting blend contains
preferably (A) in the range from 50 to 97 parts by mass, and (B) in
the range from 3 to 50 parts by mass, further preferably (A) in the
range from 60 to 95 parts by mass, and (B) in the range from 5 to
40 parts by mass, and most preferably (A) in the range from 70 to
93 parts by mass, and (B) in the range from 7 to 30 parts by mass,
based on a total of 100 parts by mass of the (A) and the (B)
described above.
[0180] Moreover, in the present invention, in addition to the
polyrotaxane being the (A) component, an iso(thio)cyanate reactive
group-containing compound (C) in which the group can react with the
(B) component can be used. The (C) component will be described
below.
[0181] <(C) Iso(Thio)Cyanate Reactive Group-Containing
Compound>
[0182] Specific examples of the iso(thio)cyanate reactive
group-containing compound can include: a poly(thi)ol compound
having two or more hydroxyl groups and/or thiol groups in one
molecule (C-1) or a mono(thi)ol compound having one hydroxyl group
or thiol group in one molecule (C-2).
[0183] <(C-1) Poly(Thi)Ol Compound Having Two or More Groups of
at Least One Kind of Group Selected from a Hydroxyl Group and a
Thiol Group in One Molecule>
[0184] A poly(thi)ol compound having two or more groups of at least
one kind of group selected from a hydroxyl group and a thiol group
in one molecule (hereinafter, also referred to simply as
"poly(thi)ol compound") is a compound having two or more (in total)
of at least one kind of group selected from the hydroxyl group (OH
group) and the thiol group (SH group) in the poly(thi)ol compound.
Among the poly(thi)ol compounds, the polyol compound is typified,
for example, by a di-, tri-, tetra-, penta- or hexa-hydroxy
compound, polyester containing two or more OH groups in one
molecule (polyester polyol), polyether containing two or more OH
groups in one molecule (hereinafter, referred to as polyether
polyol), polycarbonate containing two or more OH groups in one
molecule (polycarbonate polyol), polycaprolactone containing two or
more OH groups in one molecule (polycaprolactone polyol) and an
acrylic polymer containing two or more OH groups in one molecule
(polyacryl polyol).
[0185] Moreover, specific examples of the polythiol compound
include: aliphatic polythiol, aromatic polythiol,
halogen-substituted aromatic polythiol, heterocycle-containing
polythiol and sulfur atom-containing aromatic polythiol in addition
to a mercapto group, sulfur atom-containing aliphatic polythiol in
addition to a mercapto group, and a sulfur atom-containing
heterocycle-containing polythiol in addition to a mercapto group.
Specific examples of these compounds are as described below.
[0186] Aliphatic alcohol: ethylene glycol, diethylene glycol,
propylene glycol, dipropylene glycol, butylene glycol,
1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane,
1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane,
1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol,
glycerin, trimethylolethane, trimethylolpropane, butanetriol,
1,2-methylglucoside, pentaerythritol, dipentaerythritol,
tripentaerythritol, sorbitol, erythritol, threitol, ribitol,
arabinitol, xylitol, allitol, mannitol, dulcitol, iditol, glycol,
inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol,
polyethylene glycol, tris(2-hydroxyethyl)isocyanurate,
cyclobutanediol, cyclopentanediol, cyclohexanediol,
cycloheptanediol, cyclooctanediol, cyclohexanedimethanol,
hydroxypropylcyclohexanol,
tricyclo[5,2,1,0.sup.2.6]decane-dimethanol,
bicyclo[4,3,0]-nonanediol, dicyclohexanediol,
tricyclo[5,3,1,1.sup.3.9]dodecanediol,
bicyclo[4,3,0]nonanedimethanol,
tricyclo[5,3,1,1.sup.3.9]dodecane-diethanol, hydroxypropyl
tricyclo[5,3,1,1.sup.3.9]dodecanol, spiro[3,4]octanediol,
butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol,
maltitol, lactitol, 3-methyl-1,5-dihydroxypentane,
dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane,
2-methyl-1,3-dihydroxypropane, 1,4-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol,
o-dihydroxyxylylene, m-dihydroxyxylylene, p-dihydroxyxylylene,
1,4-bis(2-hydroxyethyl)benzene, 1,4-bis(3-hydroxypropyl)benzene,
1,4-bis(4-hydroxybutyl)benzene, 1,4-bis(5-hydroxypentyl)benzene,
1,4-bis(6-hydroxyhexyl)benzene,
2,2-bis[4-(2''-hydroxyethyloxy)phenyl]propane, as a trifunctional
polyol, TMP-30, TMP-60 and TMP-90, manufactured by Nippon Nyukazai
Co., Ltd., and as a tetrafunctional polyol, PNT40 and PNT60,
manufactured by Nippon Nyukazai Co., Ltd.
[0187] Aromatic alcohol: dihydroxynaphthalene,
trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene,
benzenetriol, biphenyltetraol, pyrogallol,
(hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A,
bisphenol F, xylylene glycol, tetrabromobisphenol A,
bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,
1,2-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane,
bis(4-hydroxyphenyl)diphenylmethane,
bis(4-hydroxyphenyl)-1-naphthylmethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,
2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)-3-methylbutane,
2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane,
2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)octane,
2,2-bis(4-hydroxyphenyl)-4-methylpentane,
2,2-bis(4-hydroxyphenyl)heptane, 4,4-bis(4-hydroxyphenyl)heptane,
2,2-bis(4-hydroxyphenyl)tridecane, 2,2-bis(4-hydroxyphenyl)octane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)propane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,
2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2,2-bis(3-allyl-4'-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)cyanomethane,
1-cyano-3,3-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)
hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)cycloheptane,
1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane,
1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane,
1,1-bis(3-methyl-4-hydroxyphenyl)-4-methylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
2,2-bis(4-hydroxyphenyl)norbornane,
2,2-bis(4-hydroxyphenyl)adamantane, 4,4'-dihydroxydiphenyl ether,
4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol
bis(4-hydroxyphenyl)ether, 4,4'-dihydroxydiphenyl sulfide,
3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
3,3'-dicyclohexyl-4,4'-dihydroxydiphenyl sulfide,
3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl sulfoxide,
3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfoxide,
4,4'-dihydroxydiphenyl sulfone,
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone,
bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3-methylphenyl)ketone,
7,7'-dihydroxy-3,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2'-spirobi(2H-
-1-benzopyran), trans-2,3-bis(4-hydroxyphenyl)-2-butene,
9,9-bis(4-hydroxyphenyl)fluorene,
3,3-bis(4-hydroxyphenyl)-2-butanone,
1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, 4,4'-dihydroxybiphenyl
and hydroquinone resorcin.
[0188] Sulfur-containing polyol:
bis-[4-(hydroxyethoxy)phenyl]sulfide,
bis-[4-(2-hydroxypropoxy)phenyl]sulfide,
bis-[4-(2,3-dihydroxypropoxy)phenyl]sulfide,
bis-[4-(4-hydroxycyclohexyloxy)phenyl]sulfide,
bis-[2-methyl-4-(hydroxyethoxy)-6-butylphenyl]sulfide, a compound
in which three or less molecules (on an average) of ethylenoxide
and/or propylene oxide per one hydroxyl group are added to the
sulfur-containing polyol, di-(2-hydroxyethyl)sulfide,
bis(2-hydroxyethyl)disulfide, 1,4-dithiane-2,5-diol,
bis(2,3-dihydroxypropyl)sulfide,
tetrakis(4-hydroxy-2-thiabutyl)methane,
bis(4-hydroxyphenyl)sulfone, tetrabromobisphenol S,
tetramethylbisphenol S, 4,4'-thiobis(6-tert-butyl-3-methylphenol)
and 1,3-bis(2-hydroxyethylthioethyl)-cyclohexane.
[0189] Sulfur-Containing Heterocyclic Polyol:
2,5-bis(hydroxymethyl)-1,4-dithiane,
3-hydroxy-6-hydroxymethyl-1,5-dithiacycloheptane and
3,7-dihydroxy-1,5-dithiacyclooctane.
[0190] Polyester polyol: a compound obtained by a condensation
reaction of polyol with polybasic acid.
[0191] Polyether polyol: a compound obtained by a reaction of a
compound having two or more active hydrogen-containing groups in a
molecule with alkylene oxide, and a modified product thereof.
[0192] Polycaprolactone polyol: a compound obtained by ring-opening
polymerization of .epsilon.-caprolactone.
[0193] Polycarbonate polyol: a compound obtained by phosgenation of
one or more kinds of low molecular-weight polyols, and a compound
obtained by a transesterification process using ethylene carbonate,
diethyl carbonate, diphenyl carbonate or the like.
[0194] Polyacryl polyol: a compound obtained from a copolymer of
hydroxyl group-containing acrylate or methacrylate with a monomer
copolymerizable with the ester.
[0195] Aliphatic polythiol: methanedithiol, 1,2-ethanedithiol,
1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,
2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol,
tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,
bicyclo[2,2,1]hepta-exo-cis-2,3-dithiol,
1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid
bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid
(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol
(2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate),
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether,
2,3-dimercaptopropyl methyl ether,
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
bis(2-mercaptoethyl)ether, ethylene glycol bis(2-mercaptoacetate),
ethylene glycol bis(3-mercaptopropionate),
1,4-bis(3-mercaptobutyryloxy)butane, 1,4-butanediol
bis(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate),
1,6-hexanediol bis(thioglycolate), tetraethylene glycol
bis(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(3-mercaptobutyrate), trimethylolpropane
tris(3-mercaptobutyrate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate),
1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, dipentaerythritol
hexakis(3-mercaptopropionate), pentaerythritol
tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane,
trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane
tris(3-mercaptobutyrate),
1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,
2-mercaptomethyl-1,3-propanedithiol,
2-mercaptomethyl-1,4-butanedithiol,
2,4,5-tris(mercaptomethyl)-1,3-dithiolane,
2,2-bis(mercaptomethyl)-1,4-butanedithiol,
4,4-bis(mercaptomethyl)-3,5-dithiaheptane-1,7-dithiol,
2,3-bis(mercaptomethyl)-1,4-butanedithiol,
2,6-bis(mercaptomethyl)-3,5-dithiaheptane-1,7-dithiol,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-bismercaptomethyl-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
[0196] Aromatic polythiol: 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene,
1,4-bis (mercaptomethyl)benzene, 1,2-bis (mercaptoethyl)benzene,
1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene,
1,2-bis (mercaptomethoxy)benzene, 1,3-bis(mercaptomethoxy)benzene,
1,4-bis(mercaptomethoxy)benzene, 1,2-bis(mercaptoethoxy)benzene,
1,3-bis(mercaptoethoxy)benzene, 1,4-bis(mercaptoethoxy)benzene,
1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene,
1,3,5-tris(mercaptoethyl)benzene,
1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris
(mercaptomethoxy)benzene, 1,3,5-tris(mercaptomethoxy)benzene,
1,2,3-tris(mercaptoethoxy)benzene,
1,2,4-tris(mercaptoethoxy)benzene,
1,3,5-tris(mercaptoethoxy)benzene, 1,2,3,4-tetramercaptobenzene,
1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis
(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptomethoxy)benzene,
1,2,4,5-tetrakis(mercaptomethoxy)benzene,
1,2,3,4-tetrakis(mercaptoethoxy)benzene,
1,2,3,5-tetrakis(mercaptoethoxy)benzene,
1,2,4,5-tetrakis(mercaptoethoxy)benzene, 2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl,
2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol,
1,5-naphthalenedithiol, 2,6-naphthalenedithiol,
2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol,
1,3-di(p-methoxyphenyl)propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol,
2,4-di(p-mercaptophenyl)pentane and
1,4-bis(mercaptopropylthiomethyl)benzene.
[0197] Halogen-substituted aromatic polythiol:
2,5-dichlorobenzene-1,3-dithiol,
1,3-di(p-chlorophenyl)propane-2,2-dithiol,
3,4,5-tribromo-1,2-dimercapto benzene and
2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene.
[0198] Heterocycle-containing polythiol:
2-methylamino-4,6-dithiol-sym-triazine,
2-ethylamino-4,6-dithiol-sym-triazine,
2-amino-4,6-dithiol-sym-triazine,
2-morpholino-4,6-dithiol-sym-triazine,
2-cyclohexylamino-4,6-dithiol-sym-triazine,
2-methoxy-4,6-dithiol-sym-triazine,
2-phenoxy-4,6-dithiol-sym-triazine,
2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
2-thiobutyloxy-4,6-dithiol-sym-triazine and
1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trio-
ne.
[0199] Sulfur atom-containing aromatic polythiol in addition to a
mercapto group: 1,2-bis(mercaptomethylthio)benzene,
1,3-bis(mercaptomethylthio)benzene,
1,4-bis(mercaptomethylthio)benzene,
1,2-bis(mercaptoethylthio)benzene, 1,3-bis
(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene,
1,2,3-tris(mercaptomethylthio)benzene,
1,2,4-tris(mercaptomethylthio)benzene,
1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris
(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene,
1,3,5-tris(mercaptoethylthio)benzene,
1,2,3,4-tetrakis(mercaptomethylthio)benzene,
1,2,3,5-tetrakis(mercaptomethylthio)benzene,
1,2,4,5-tetrakis(mercaptomethylthio)benzene,
1,2,3,4-tetrakis(mercaptoethylthio)benzene,
1,2,3,5-tetrakis(mercaptoethylthio)benzene and
1,2,4,5-tetrakis(mercaptoethylthio)benzene.
[0200] Sulfur atom-containing aliphatic polythiol in addition to a
mercapto group: bis(mercaptomethyl)sulfide,
bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide,
bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio) methane,
bis(3-mercaptopropyl) methane, 1,2-bis(mercaptomethylthio)ethane,
1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,3-bis(3-mercaptopropylthio)propane,
1,2-bis(2-mercaptoethylthio)-3-mercaptopropane,
2-mercaptoethylthio-1,3-propanedithiol,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,
bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)disulfide, an ester of thioglycolic acid or
mercaptopropionic acid of the compound, hydroxymethylsulfide
bis(2-mercaptoacetate), hydroxymethylsulfide
bis(3-mercaptopropionate), hydroxyethylsulfide
bis(2-mercaptoacetate), hydroxyethylsulfide
bis(3-mercaptopropionate), hydroxypropylsulfide
bis(2-mercaptoacetate), hydroxypropylsulfide
bis(3-mercaptopropionate), hydroxymethyldisulfide
bis(2-mercaptoacetate), hydroxymethyldisulfide
bis(3-mercaptopropionate), hydroxyethyldisulfide
bis(2-mercaptoacetate), hydroxyethyldisulfide
bis(3-mercaptopropionate), hydroxypropyldisulfide
bis(2-mercaptoacetate), hydroxypropyldisulfide
bis(3-mercaptopropionate), 2-mercaptoethylether
bis(2-mercaptoacetate), 2-mercaptoethylether
bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol
bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol
bis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane,
2,5-bis(2-mercaptoethyl)-1,4-dithiane,
2,5-bis(3-mercaptopropyl)-1,4-dithiane,
2-(2-mercaptoethyl)-5-mercaptomethyl-1,4-dithiane,
2-(2-mercaptoethyl)-5-(3-mercaptopropyl)-1,4-dithiane,
2-mercaptomethyl-5-(3-mercaptopropyl)-1,4-dithiane, thioglycolic
acid bis(2-mercaptoethyl ester), thiodipropionic acid
bis(2-mercaptoethyl ester), 4,4'-thiodibutyl acid
bis(2-mercaptoethyl ester), dithiodiglycolic acid
bis(2-mercaptoethyl ester), dithiodipropionic acid
bis(2-mercaptoethyl ester), 4,4'-dithiodibutyl acid
bis(2-mercaptoethyl ester), thiodiglycol acid
bis(2,3-dimercaptopropyl ester), thiodipropionic acid
bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid
bis(2,3-dimercaptopropyl ester), dithiodipropionic acid
(2,3-dimercaptopropyl ester),
2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane,
4,5-bis(mercaptomethylthio)-1,3-dithiolane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-bis(mercaptomethylthio)methyl-1,3-dithietane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane,
1,2,7-trimercapto-4,6-dithiaheptane,
1,2,9-trimercapto-4,6,8-trithianonan,
1,2,11-trimercapto-4,6,8,10-tetrathiaundecane,
1,2,13-trimercapto-4,6,8,10,12-pentathiatridecane,
1,2,8,9-tetramercapto-4,6-dithianonane,
1,2,10,11-tetramercapto-4,6,8-trithiaundecane,
1,2,12,13-tetramercapto-4,6,8,10-tetrathiatridecane,
bis(2,5-dimercapto-4-thiapentyl)disulfide,
bis(2,7-dimercapto-4,6-dithiaheptyl)disulfide,
1,2,5-trimercapto-4-thiapentane,
3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane,
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane,
3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane,
3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,
3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,
4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane,
3-mercaptomethyl-1,6-dimercapto-2,5-dithiahexane,
3-mercaptomethylthio-1,5-dimercapto-2-thiapentane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,4,8,11-tetramercapto-2,6,10-trithiaundecane,
1,4,9,12-tetramercapto-2,6,7,11-tetrathiadodecane,
2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol,
2,3,5,6,8,9-hexathia-,10-decanedithiol,
2-(1-mercapto-2-mercaptomethyl-3-thiabutyl)-1,3-dithiolane,
1,5-dimercapto-3-mercaptomethylthio-2,4-dithiapentane,
2-mercaptomethyl-4-mercapto-1,3-dithiolane,
2,5-dimercapto-1,4-dithiane, 2,6-dimercapto-1,4-dithiane,
2,4-dimercaptomethyl-1,3-dithietane,
1,2,6,10,11-pentamercapto-4,8-dithiaundecane,
1,2,9,10-tetramercapto-6-mercaptomethyl-4,7-dithiadecane,
1,2,9,13,14-pentamercapto-6-mercaptomethyl-4,7,11-trithiatetradecane,
1,2,6,10,14,15-hexamercapto-4,8,12-trithiapentadecane,
1,4-dithiane-2,5-bis(4,5-dimercapto-2-thiapentane) and
1,4-dithiane-2,5-bis(5,6-dimercapto-2,3-dithiahexane).
[0201] Sulfur atom-containing heterocycle-containing polythiol in
addition to a mercapto group: 3,4-thiophenedithiol,
tetrahydrothiophene-2,5-dimercaptomethyl and
2,5-dimercapto-1,3,4-thiadiazole.
[0202] Isocyanurate group-containing polythiol:
1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,
tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate,
1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trio-
ne and tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.
[0203] Moreover, as the (C-1) component in the present invention, a
compound having one or more hydroxyl groups and thiol groups each
in one molecule can also be used. Specific examples thereof can
include the following compounds.
[0204] 2-Mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin
di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane,
2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol,
1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol,
1,2-dimercapto-1,3-butanediol, pentaerythritol
tris(3-mercaptopropionate), pentaerythritol
mono(3-mercaptopropionate), pentaerythritol
bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate),
pentaerythritol pentakis(3-mercaptopropionate),
hydroxymethyl-tris(mercaptoethylthiomethyl)methane,
1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4'-mercaptodiphenylsulfone,
2-(2-mercaptoethylthio)ethanol, dihydroxyethylsulfide
mono(3-mercaptopropionate), dimercaptoethane mono(salicylate) and
hydroxyethylthiomethyl-tris(mercaptoethylthio)methane.
[0205] As the (C-1) component, a compound having a silsesquioxane
structure can be used in addition thereto. The silsesquioxane is a
compound represented by the following formula (5).
[Formula 14]
(R.sup.6--SiO.sub.3/2).sub.n (5)
[0206] {where, a plurality of R.sup.6 are any of an organic group
containing a hydroxyl group and/or thiol group, a hydrogen atom, an
alkyl group, a cycloalkyl group, an alkoxy group or a phenyl group,
which may be the same with or different from each other, and have
two or more the organic group containing the hydroxyl group and/or
thiol group in at least one molecule, and a degree of
polymerization n is an integer from 6 to 100.}.
[0207] The organic group containing the hydroxyl group and/or thiol
group in R.sup.6 in the formula (5) is a monovalent hydrocarbon
group having at least one hydroxyl group and/or thiol group bound
thereto and having 1 to 10 carbon atoms, or a monovalent group
containing an oxygen atom or a sulfur atom in a chain having at
least one hydroxyl group and/or thiol group bound thereto and
having 1 to 10 carbons. Specifically, preferred examples include an
alkylene chain having 1 to 10 carbon atoms, and an organic group
derived from polyol, polythiol or the like.
[0208] Moreover, the alkyl group in R.sup.6 is preferably an alkyl
group having 1 to 10 carbon atoms. Specific examples of the alkyl
group having 1 to 10 carbon atoms include a methyl group, an ethyl
group, a n-propyl group, an isopropyl group, a n-butyl group, a
sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl
group, a n-octyl group and an isooctyl group.
[0209] The cycloalkyl group is preferably a cycloalkyl group having
3 to 8 carbon atoms. Specific examples of the cycloalkyl group
having 3 to 8 carbon atoms include a cyclopropyl group, a
cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a
cycloheptyl group and a cyclooctyl group.
[0210] The alkoxy group is preferably an alkoxy group having 1 to 6
carbon atoms. Specific examples of the alkoxy group having 1 to 6
carbon atoms include a methoxy group, an ethoxy group, a n-propoxy
group, an isopropoxy group, a n-butoxy group, a sec-butoxy group
and a tert-butoxy group.
[0211] In general, a silsesquioxane compound can take various
structures such as a cage-like structure, a ladder-like structure
and a random structure, but in the present invention, the
silsesquioxane compound is preferably a mixture formed of a
plurality of structures.
Preferred Examples of (C-1) Component
[0212] Preferred examples of the poly(thi)ol compound being the
(C-1) component include: polyethylene polyol, polycaprolactone
polyol, polycarbonate polyol, trimethylolpropane, pentaerythritol,
trimethylolpropane tris(3-mercaptopropionate), pentaerythritol
tetrakis(3-mercaptopropionate), dipentaerythritol
hexakis(3-mercaptopropionate), tetraethylene glycol
bis(3-mercaptopropionate), 1,4-butanediol
bis(3-mercaptopropionate), 1,6-hexandiol bis(3-mercaptopropionate),
1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,
2,2-bis(mercaptomethyl)-1,4-butanedithiol,
1,4-bis(mercaptopropylthiomethyl)benzene,
2,5-bis(mercaptomethyl)-1,4-dithiane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
1,1,1,1-tetrakis(mercaptomethyl)methane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-mercaptomethanol and
tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.
[0213] Next, (C-2) mono(thi)ol compound having one hydroxyl group
or one thiol group in one molecule will be described.
[0214] <(C-2) Mono(Thi)Ol Compound Having One Hydroxyl Group or
One Thiol Group in One Molecule>
[0215] In the present invention, the mono(thi)ol compound having
one hydroxyl group or one thiol group in one molecule (hereinafter,
also referred to simply as "mono(thi)ol compound") can be used. If
the optical composition according to the present invention is
cured, a rigid cured body of a network structure having a
(thio)urethane bond can be obtained by a reaction of the
polyiso(thio)cyanate compound with the poly(thi)ol compound.
Further, a mono(thi)ol compound having one end-free structure is
incorporated into the network structure by blending the (C-2)
component into the optical composition, and therefore a flexible
space is formed in the periphery of the mono(thi)ol compound.
Accordingly, the reversible structural change of the photochromic
compound existing in the vicinity of the space is further
immediately caused, and therefore the photochromic cured body
having excellent photochromic characteristics (the color optical
density and the color fading rate) can be conceivably produced.
[0216] Further, the mono(thi)ol compound has only one hydroxyl
group or only one thiol group, and therefore an amount of a
hydrogen bond is smaller than an amount in the poly(thi)ol
compound. As a result, the mono(thi)ol compound has a high effect
on reducing viscosity of the optical composition.
[0217] Specific examples of the mono(thi)ol compound can include
the compounds described below.
[0218] Compound having one hydroxyl group in one molecule:
polyethylene glycol monooleyl ether, polyoxyethylene oleate,
polyethylene glycol monolaurate, polyethylene glycol monostearate,
polyethylene glycol mono-4-octylphenyl ether, straight-chain
polyoxyethylene alkyl ether (polyethylene glycol monomethyl ether,
polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether,
polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether,
polyoxyethylene stearyl ether), and saturated alkyl alcohol having
a straight-chain or branched-chain shape and having 5 to 30 carbon
atoms.
[0219] Compound having one thiol group in one molecule:
3-methoxybutyl thioglycolate, 2-ethylhexyl thioglycolate,
2-mercaptoethyl octanoate, 3-methoxybutyl 3-mercaptopropionate,
3-methoxybutyl thioglycolate, ethyl 3-mercaptopropionate, 2-octyl
3-mercaptopropionate, n-octyl-3-mercaptopropionate,
methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate,
stearyl-3-mercaptopropionate and saturated alkyl thiol having a
straight-chain or branched-chain structure and having 5 to 30
carbon atoms.
[0220] <Preferred Blending Proportion of (A), (B) and (C)
Components>
[0221] Further, in the optical composition according to the present
invention, with regard to an optimum blending proportion of the
(A), (B) and (C) components described above for obtaining excellent
moldability, mechanical strength and hardness in the optical
article or excellent photochromic characteristics upon adding the
photochromic compound thereto, to be described later, the resulting
blend contains preferably (A) in the range from 3 to 15 parts by
mass, (B) in the range from 25 to 70 parts by mass, and (C) in the
range from 20 to 65 parts by mass, and most preferably (A) in the
range from 4 to 10 parts by mass, (B) in the range from 30 to 60
parts by mass, and (C) in the range from 30 to 60 parts by mass,
when a total of the (A), (B) and (C) components described above is
taken as 100 parts by mass.
[0222] <(D) Photochromic Compound>
[0223] The optical composition to which the photochromic compound
is added according to the present invention can be used as a
photochromic optical composition.
[0224] As the photochromic compound exhibiting the photochromism,
publicly-known compounds per se can be used, and these compounds
can be used alone, or in combination with two or more kinds
thereof. The plastic lens having the photochromic characteristics
can be produced by adding these compounds to the optical
composition and causing polymerization curing of the resulting
material.
[0225] Typified materials as such a photochromic compound include a
fulgide compound, a chromene compound and a spirooxazine compound,
and are disclosed in a lot of literature, such as JP-H2-28154 A,
JP-S62-288830 A, WO 94/22850 A and WO 96/14596 A, for example.
[0226] In the present invention, among the publicly-known
photochromic compounds, from a viewpoint of the photochromism such
as color optical density, initial coloring properties, durability
and a color fading rate, a chromene compound having an
indeno[2,1-f]naphtho[1,2-b]pyran skeleton is further preferably
used, and a chromene compound having a molecular weight of 540 or
more is particularly preferably used because the compound is
particularly excellent in the color optical density and the color
fading rate.
[0227] The chromene compounds shown below are examples of the
chromene compounds particularly preferably used in the present
invention.
##STR00013##
[0228] <Preferred Composition of the Photochromic Optical
Composition>
[0229] In the optical composition according to the present
invention, a preferred amount of use thereof is different also
depending on a method for developing the photochromism. Upon
polymerizing the composition into the photochromic cured body by
the kneading method, when the photochromism of the photochromic
cured body are developed, the photochromic compound (D) is used
preferably in an amount from 0.0001 to 10 parts by mass, further
preferably in an amount from 0.001 to 2 parts by mass, and most
preferably in an amount from 0.001 to 1 part by mass, based on a
total of 100 parts by mass of the (A) component, the (B) component
and the (C) component. Moreover, when the photochromism is
developed by the lamination method, the photochromic compound (D)
is used preferably in an amount from 0.01 to 20 parts by mass, and
further preferably in an amount from 0.01 to 10 parts by mass.
Moreover, when the photochromism is developed by the binder method,
the component (D) is used preferably in an amount from 0.1 to 40
parts by mass, and further preferably from 0.5 to 20 parts by
mass.
[0230] <(E) Resin Modifier, (F) Polymerization Curing
Accelerator or (G) Internal Mold Release Agent>
[0231] In the optical composition according to the present
invention, in addition to each component of (A), (B) and (C), the
optical composition may further contain a resin modifier (E), a
polymerization curing accelerator (F) or an internal mold release
agent (G) for the purpose of improving a refractive index,
moldability, adjusting hardness of the cured body and the like.
These materials will be described.
[0232] <(E) Resin Modifier>
[0233] In the present invention, the resin modifier can be added
thereto for the purpose of improving the refractive index of the
cured body to be obtained, or adjusting the hardness thereof.
Specific examples include an episulfide-based compound, a
thietanyl-based compound, an epoxy compound and an olefin compound
containing a (meth)acrylate compound. Specific examples will be
described below.
[0234] <Episulfide-Based Compound>
[0235] The episulfide-based compound is a compound having two or
more episulfide groups in one molecule, and is cured by the
ring-opening polymerization. These compounds may be added thereto
for achieving a high refractive index. Specific examples of such an
episulfide compound can include compounds described below.
[0236] Bis(1,2-epithioethyl)sulfide,
bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide,
bis(2,3-epithiopropylthio)methane, bis(2,3-epithiopropyl)disulfide,
bis(2,3-epithiopropyldithio)methane,
bis(2,3-epithiopropyldithio)ethane,
bis(6,7-epithio-3,4-dithiaheptyl)sulfide,
bis(6,7-epithio-3,4-dithiaheptyl)disulfide,
1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl),
1,3-bis(2,3-epithiopropyldithiomethyl)benzene,
1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthi-
o)-4-thiahexane, 1,2,3-tris(2,3-epithiopropyldithio)propane,
1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane,
1,3-bis(2,3-epithiopropyldithio)-2-thiapropane,
1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane,
1,1,1-tris(2,3-epithiopropyldithio) methane,
1,1,1-tris(2,3-epithiopropyldithiomethylthio)methane,
1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane,
1,1,2,2-tetrakis(2,3-epithiopropyldithiomethylthio)ethane,
1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane,
1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane,
2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane and
2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1,3-dithietane.
[0237] <Thietanyl-Based Compound>
[0238] The thietanyl-based compound is a thietane compound having
two or more thietanyl groups in one molecule, and is cured by the
ring-opening polymerization. These compounds may be added thereto
for achieving the high refractive index. A part of such a thietanyl
compound has an episulfide group together with a plurality of
thietanyl groups, which are listed in the section of the
episulfide-based compound described above. Other thietanyl
compounds include a metal-containing thietane compound having a
metal atom in the molecule, and a non-metal thietane compound
containing no metal therein. Specific examples of such a thietanyl
compound can include the compounds described below.
[0239] Non-metal thietane compound: bis(3-thietanyl)disulfide,
bis(3-thietanyl)sulfide, bis(3-thietanyl)trisulfide,
bis(3-thietanyl)tetrasulfide,
1,4-bis(3-thietanyl)-1,3,4-trithiabutane,
1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane,
1,6-bis(3-thietanyl)-1,3,4,6-tetrathiahexane,
1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane,
1,7-bis(3-thietanyl)-1,2,4,5,7-pentathiaheptane,
1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane,
1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane,
1,2,3-tris(3-thietanylthio)propane,
1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithia
octane,
1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane,
1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trit-
hiaundecane,
1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,
2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,
2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane,
bisthietanyl sulfide, bis(thietanylthio)methane,
3-[<(thietanylthio)methylthio>methylthio]thiethane,
bisthietanyl disulfide, bisthietanyl trisulfide, bisthietanyl
tetrasulfide, bisthietanyl pentasulfide,
1,4-bis(3-thietanyldithio)-2,3-dithiabutane,
1,1,1-tris(3-thietanyldithio)methane,
1,1,1-tris(3-thietanyldithiomethylthio)methane,
1,1,2,2-tetrakis(3-thietanyldithio)ethane and
1,1,2,2-tetrakis(3-thietanyldithiomethylthio)ethane.
[0240] <Metal-Containing Thietane Compound>
[0241] This thietane compound contains a Group 14 element such as a
Sn atom, a Si atom, a Ge atom and a Pb atom; a Group 4 element such
as a Zr atom and a Ti atom; a Group 13 element such as an Al atom;
or a Group 12 element such as a Zn atom, as a metal atom in the
molecule. For example, the compounds described below are
particularly preferably used.
[0242] Alkylthio(thietanylthio)tin: methylthio
tris(thietanylthio)tin, ethylthio tris(thietanylthio)tin,
propylthio tris(thietanylthio)tin and isopropylthio
tris(thietanylthio)tin.
[0243] Bis(alkylthio)bis(thietanylthio)tin: bis(methylthio)bis
(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin,
bis(propylthio)bis(thietanylthio)tin and
bis(isopropylthio)bis(thietanylthio)tin.
[0244] Alkylthio(alkylthio)bis(thietanylthio)tin:
ethylthio(methylthio)bis (thietanylthio)tin,
methylthio(propylthio)bis(thietanylthio)tin,
isopropylthio(methylthio)bis(thietanylthio)tin,
ethylthio(propylthio)bis(thietanylthio)tin,
ethylthio(isopropylthio)bis(thietanylthio)tin and isopropylthio
(propylthio)bis (thietanylthio)tin.
[0245] Bis(thietanylthio)cyclic dithiotin compound:
bis(thietanylthio)dithiastannetane,
bis(thietanylthio)dithiastannolane,
bis(thietanylthio)dithiastanninane and
bis(thietanylthio)trithiastannokane.
[0246] Alkyl(thietanylthio)tin compound: methyl
tris(thietanylthio)tin, dimethyl bis(thietanylthio)tin, butyl
tris(thietanylthio)tin, tetrakis(thietanylthio)tin, tetrakis
(thietanylthio) germanium and tris(thietanylthio)bismuth.
[0247] <Epoxy Compound>
[0248] The epoxy compound has an epoxy group as a polymerizable
group in the molecule, and is cured by the ring-opening
polymerization. These compounds may be added thereto for adjusting
the refractive index and the hardness of the lens. Such an epoxy
compound is generally classified into an aliphatic epoxy compound,
an alicyclic epoxy compound and an aromatic epoxy compound, and
specific examples thereof can include the compounds described
below.
[0249] Aliphatic epoxy compound: ethylene oxide, 2-ethyl oxirane,
butyl glycidyl ether, phenyl glycidyl ether, 2,2'-methylene bis
oxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol
diglycidyl ether, diethylene glycol diglycidyl ether, triethylene
glycol diglycidyl ether, tetraethylene glycol diglycidyl ether,
nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl
ether, dipropylene glycol diglycidyl ether, tripropylene glycol
diglycidyl ether, tetrapropylene glycol diglycidyl ether,
nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl
ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl
ether, diglycerol tetraglycidyl ether, pentaerythritol
tetraglycidyl ether, diglycidyl ether of
tris(2-hydroxyethyl)isocyanurate and triglycidyl ether of
tris(2-hydroxyethyl)isocyanurate.
[0250] Alicyclic epoxy compound: isophoronediol diglycidyl ether
and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.
[0251] Aromatic epoxy compound: resorcin diglycidyl ether,
bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
bisphenol S diglycidyl ether, o-phthalic acid diglycidyl ester,
phenol novolak polyglycidyl ether and cresol novolak polyglycidyl
ether.
[0252] Moreover, in addition to the compounds described above, an
epoxy compound having a sulfur atom together with an epoxy group in
the molecule can also be used. Such a sulfur atom-containing epoxy
compound particularly contributes to improvement in the refractive
index, and includes a chain aliphatic group-based compound and a
cyclic aliphatic group-based compound. Specific examples thereof
are as described below.
[0253] Chain aliphatic group-based sulfur atom-containing epoxy
compound: bis(2,3-epoxypropyl)sulfide,
bis(2,3-epoxypropyl)disulfide, bis(2,3-epoxypropylthio)methane,
1,2-bis(2,3-epoxypropylthio)ethane,
1,2-bis(2,3-epoxypropylthio)propane,
1,3-bis(2,3-epoxypropylthio)propane,
1,3-bis(2,3-epoxypropylthio)-2-methylpropane,
1,4-bis(2,3-epoxypropylthio)butane,
1,4-bis(2,3-epoxypropylthio)-2-methylbutane,
1,3-bis(2,3-epoxypropylthio)butane,
1,5-bis(2,3-epoxypropylthio)pentane,
1,5-bis(2,3-epoxypropylthio)-2-methylpentane,
1,5-bis(2,3-epoxypropylthio)-3-thiapentane,
1,6-bis(2,3-epoxypropylthio)hexane,
1,6-bis(2,3-epoxypropylthio)-2-methylhexane,
3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane,
1,2,3-tris(2,3-epoxypropylthio)propane,
2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane
and
2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane.
[0254] Cyclic aliphatic group-based sulfur atom-containing epoxy
compound: 1,3-bis(2,3-epoxypropylthio)cyclohexane,
1,4-bis(2,3-epoxypropylthio)cyclohexane,
1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane,
1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane,
2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane,
2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithian
e and
2,5-bis(2,3-epoxy-propylthiomethyl)-2,5-dimethyl-1,4-dithiane.
[0255] <Olefin Compound Containing a (Meth)Acrylate Compound,
and Compounds Having Other Radical Polymerizable Groups>
[0256] An olefin compound containing a (meth)acrylate compound and
compounds having other radical polymerizable groups each have a
radical polymerizable group as a polymerizable group in the
molecule, and are cured by the radical polymerization. These
compounds can be used for adjusting the hardness of the lens, and
specific examples thereof can include compound described below.
[0257] (Meth)acrylate compound: ethylene glycol diacrylate,
ethylene glycol dimethacrylate, diethylene glycol diacrylate,
diethylene glycol dimethacrylate, triethylene glycol diacrylate,
triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
tetraethylene glycol dimethacrylate, polyethylene glycol
diacrylate, polyethylene glycol dimethacrylate, propylene glycol
diacrylate, propylene glycol dimethacrylate, dipropylene glycol
diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol
diacrylate, tripropylene glycol dimethacrylate, polypropylene
glycol dimethacrylate, polypropylene glycol diacrylate, neopentyl
glycol diacrylate, neopenthyl glycol dimethacrylate, ethylene
glycol bisglycidyl acrylate, ethylene glycol bisglycidyl
methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate,
2,2-bis(4-acryloxyethoxyphenyl)propane,
2,2-bis(4-methacryloxyethoxyphenyl)propane,
2,2-bis(4-acryloxydiethoxyphenyl)propane,
2,2-bis(4-methacryloxydiethoxyphenyl)propane,
2,2-bis(4-methacryloyloxyethoxyphenyl)propane,
2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane,
2,2-bis(4-methacryloyloxydipropoxyphenyl)propane, bisphenol F
diacrylate, bisphenol F dimethacrylate,
1,1-bis(4-acryloxyethoxyphenyl)methane,
1,1-bis(4-methacryloxyethoxyphenyl)methane,
1,1-bis(4-acryloxydiethoxyphenyl)methane,
1,1-bis(4-methacryloxydiethoxyphenyl)methane,
dimethyloltricyclodecane diacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate,
ditrimethylolpropane tetraacrylate, ditrimethylolpropane
tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate,
pentaerythritol triacrylate, pentaerythritol tetraacrylate,
pentaerythritol tetramethacrylate, methylthio acrylate, methylthio
methacrylate, phenylthio acrylate, benzylthio methacrylate,
xylylenedithiol diacrylate, xylylenedithiol dimethacrylate,
mercaptoethylsulfide diacrylate, mercaptoethylsulfide
dimethacrylate, bifuntional urethane acrylate and bifunctional
urethane methacrylate.
[0258] Allyl compound: allyl glycidyl ether, diallyl phthalate,
diallyl terephthalate, diallyl isophthalate, diallyl carbonate,
diethylene glycol bis allyl carbonate and methoxy polyethylene
glycol allyl ether.
[0259] Vinyl compound: .alpha.-methylstyrene, an
.alpha.-methylstyrene dimer, styrene, chlorostyrene, methylstyrene,
bromostyrene, dibromostyrene, divinylbenzene and 3,9-divinyl
spirobi(m-dioxane).
[0260] <(F) Polymerization Curing Accelerator>
[0261] In the optical composition according to the present
invention, various polymerization curing accelerators can be used
for immediately accelerating the polymerization curing according to
a kind of the compound described above.
[0262] For example, when the accelerator is used for a reaction of
the hydroxyl group and the thiol group with a NCO group and a NCS
group, a reaction catalyst for urethane or urea or a condensation
agent is used as the polymerization curing accelerator.
[0263] When the episulfide-based compound, the thietanyl-based
compound or the epoxy compound is used therefor, a cationic
polymerization catalyst for allowing the ring-opening
polymerization of an epoxy curing agent or the epoxy group is used
as the polymerization curing accelerator.
[0264] When the composition contains a compound having a
(meth)acryl group, and other radical polymerizable groups (the
olefin compound containing the (meth)acrylate compound and the
compounds having other radical polymerizable groups), a radical
polymerization initiator is used as the polymerization curing
accelerator.
[0265] <Reaction Catalyst for Urethane or Urea>
[0266] This reaction catalyst is used in formation of a
poly(thio)urethane bond by a reaction of polyiso(thia)cyanate with
polyol or polythiol. Specific examples of these polymerization
catalysts include tertiary amines and inorganic or organic salts
corresponding thereto, phosphines, quaternary ammonium salts,
quaternary phosphonium salts, Lewis acids or organic sulfonic
acid.
[0267] Specific examples thereof can include the compounds
described below. Moreover, when catalyst activity is excessively
high depending on a kind of the compound to be selected as
described above, the catalyst activity can be suppressed by mixing
tertiary amine and Lewis acid and using the resulting mixture.
[0268] Tertiary amines: triethylamine, tri-n-propylamine,
triisopropylamine, tri-n-butylamine, triisobutylamine,
triethylamine, hexamethylenetetramine, N,N-dimethyloctylamine,
N,N,N',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylene
bis(1-methylpiperidine) and
1,8-diazabicyclo-(5,4,0)-7-undecene.
[0269] Phosphines: trimethylphosphine, triethylphosphine,
tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
triphenylphosphine, tribenzylphosphine,
1,2-bis(diphenylphosphino)ethane and
1,2-bis(dimethylphosphino)ethane.
[0270] Quaternary ammonium salts: tetramethylammonium bromide,
tetrabutylammonium chloride and tetrabutylammonium bromide.
[0271] Quaternary phosphonium salts: tetramethylphosphonium
bromide, tetrabutylphosphonium chloride and tetrabutylphosphonium
bromide.
[0272] Lewis acid: triphenyl aluminum, dimethyltin dichloride,
dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride,
dibutyltin dilaurate, dibutyltin maleate, a dibutyltin maleate
polymer, dibutyltin diricinolate, dibutyltin
bis(dodecylmercaptide), dibutyltin bis(isooctylthioglycolate),
dioctyltin dichloride, dioctyltin maleate, a dioctyltin maleate
polymer, dioctyltin bis(butylmaleate), dioctyltin dilaurate,
dioctyltin diricinolate, dioctyltin dioleate, dioctyltin
di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate),
didodecyltin diricinolate; and various metal salts such as copper
oleate, copper acetylacetonate, iron acetylacetonate, iron
naphthenate, iron lactate, iron citrate, iron gluconate, potassium
octoate and 2-ethylhexyl titanate.
[0273] Organic sulfonic acid: methanesulfonic acid, benzenesulfonic
acid and p-toluenesulfonic acid.
[0274] <Condensation Agent>
[0275] Specific examples of the condensation agent can include the
compounds described below.
[0276] Inorganic acid: hydrogen chloride, hydrogen bromide,
sulfuric acid and phosphoric acid.
[0277] Organic acid: p-toluenesulfonic acid and camphorsulfonic
acid.
[0278] Acidic ion-exchange resin: Amberlite and Amberlyst.
[0279] Carbodiimide: dicyclohexylcarbodiimide and
1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.
[0280] <Epoxy Curing Agent>
[0281] Specific examples of the epoxy curing agent can include the
compounds described below.
[0282] Amine compound and salt thereof: 2-methylimidazole,
2-ethyl-4-methylimidazole,
1,8-diaza-bicyclo(5,4,0)undecene-7-trimethylamine,
benzyldimethylamine, triethylamine,
2,4,6-tris(dimethylaminomethyl)phenol and
2-(dimethylaminomethyl)phenol.
[0283] Quaternary ammonium salt: tetramethylammonium chloride,
benzyltrimethylammonium bromide and tetrabutylammonium bromide.
[0284] Organic phosphine compound: tetra-n-butylphosphonium
benzotriazolate and tetra-n-butylphosphonium-o,o-diethyl
phosphorodithioate.
[0285] Metal carboxylate: chromium(III) tricarboxylate and tin
octylate.
[0286] Acetylacetone chelate compound: chromium
acetylacetonate.
[0287] <Cationic Polymerization Catalyst>
[0288] Specific examples of the cationic polymerization catalyst
can include the compounds described below.
[0289] Lewis acid-based catalyst: a BF.sub.3-amine complex,
PF.sub.5, BF.sub.3, AsF.sub.5 and SbF.sub.5.
[0290] Thermosetting cationic polymerization catalyst: a
phosphonium salt or a quaternary ammonium salt, a sulfonium salt,
abenzylammonium salt, a benzylpyridinium salt, a benzylsulfonium
salt, a hydrazinium salt, carboxylate, sulfonate and
amineimide.
[0291] Ultraviolet curable cationic polymerization catalyst:
diaryliodonium hexafluorophosphate and bis(dodecylphenyl)iodonium
hexafluoroantimonate.
[0292] <Radical Polymerization Initiator>
[0293] The polymerization initiator includes a thermal
polymerization initiator, and specific examples are as described
below.
[0294] Diacyl peroxide: benzoyl peroxide, p-chlorobenzoyl peroxide,
decanoyl peroxide and lauroyl peroxide.
[0295] Acetyl peroxide peroxyester: t-butylperoxy-2-ethyl hexanate,
t-butylperoxy neodecanoate, cumylperoxy neodecanoate and
t-butylperoxy benzoate.
[0296] Percarbonate: diisopropyl peroxydicarbonate and di-sec-butyl
peroxydicarbonate.
[0297] Azo compound: azobisisobutyronitrile.
[0298] The various polymerization curing accelerators (E) described
above each can be used alone or in combination with two or more
kinds, and an amount of use thereof may be a so-called "catalyst
amount". For example, the amount may be as small as in the range
from 0.001 to 10 parts by mass, and particularly from 0.01 to 5
parts by mass, based on a total of 100 parts by mass of the (A),
(B) and (C) described above.
[0299] <(G) Internal Mold Release Agent>
[0300] As an example of the internal mold release agent used in the
present invention, any agent can be used, as long as the agent has
an effect of releasability and does not adversely affect physical
properties of the resin, such as transparency, and a surfactant is
preferably used. Above all, a phosphate-based surfactant is
preferable. The internal mold release agent herein also includes an
agent that exhibits a releasing effect among the various catalysts
described above, and includes, for example, quaternary ammonium
salts and quaternary phosphonium salts in several cases. These
internal mold release agents are appropriately selected depending
on a combination with a monomer, polymerization conditions,
economic efficiency, and ease of handling. Specific examples of the
internal mold release agent of the phosphate are as described
below.
[0301] Alkyl acid phosphate: mono-n-butyl phosphate,
mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl
phosphate, bis(2-ethylhexyl)phosphate, di(2-ethylhexyl)phosphate,
di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate
(mono- and di-mixture), ethyl acid phosphate (mono- and
di-mixture), butoxyethyl acid phosphate (mono- and di-mixture),
2-ethylhexyl acid phosphate (mono- and di-mixture), isotridecyl
acid phosphate (mono- and di-mixture), tetracosyl acid phosphate
(mono- and di-mixture) and stearyl acid phosphate (mono- and
di-mixture).
[0302] Other phosphates: oleyl acid phosphate (mono- and
di-mixture), dibutyl pyrophosphate, ethylene glycol acid phosphate
(mono- and di-mixture) and butoxyethyl acid phosphate (mono- and
di-mixture).
[0303] The various internal mold release agents (G) described above
each can be used alone or in combination with two or more kinds,
and an amount of use thereof may be small. For example, the
internal mold release agent can be used in an amount from 0.001 to
10 parts by mass based on a total of 100 parts by mass of (A), (B)
and (C).
[0304] <Other Blending Components>
[0305] Upon adding the photochromic compound to the optical
composition according to the present invention, publicly-known
various blending agents per se can be blended, when necessary,
within the range in which advantageous effects of the present
invention are not adversely affected. For example, various
stabilizers such as an ultraviolet absorber, an antistatic agent,
an infrared absorber, an ultraviolet stabilizer, an antioxidant, a
coloring inhibitor, an antistatic agent, a fluorescent dye, a dye,
a pigment and a flavoring agent, and an additive, a solvent, a
leveling agent, and further thiols such as t-dodecylmercaptan as a
polymerization modifier can be added thereto.
[0306] Above all, if the ultraviolet stabilizer is used therefor,
durability of the photochromic compound can be improved, and
therefore such use is preferable. As such an ultraviolet
stabilizer, a hindered amine light stabilizer, a hindered phenol
antioxidant, a sulfur-type antioxidant or the like is known.
Particularly preferred ultraviolet stabilizers are as described
below.
[0307] Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, ADK STAB
LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82 and LA-87,
manufactured by ADEKA Corporation, 2,6-di-t-butyl-4-methyl-phenol,
ethylene
bis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], and
IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520,
259, 3114, 3790, 5057 and 565, manufactured by Ciba Specialty
Chemicals Co., Ltd.
[0308] An amount of use of such an ultraviolet stabilizer is not
particularly limited, as long as the advantageous effects of the
present invention are not adversely affected, but the amount is
ordinarily in the range from 0.001 part by mass to 10 parts by
mass, and particularly in the range from 0.01 part by mass to 1
part by mass, based on a total of 100 parts by mass of (A), (B) and
(C). In particular, when the hindered amine light stabilizer is
used, an effect of improving the durability is different depending
on a kind of the photochromic compound. As a result, in order to
avoid occurrence of color shift of an adjusted coloring tone, the
amount should be adjusted to an amount from 0.5 to 30 mol, further
preferably from 1 to 20 mol, and still further preferably from 2 to
15 mol per one mol of the photochromic compound (D).
[0309] Moreover, specific examples of the antistatic agent include
an alkali metal or alkaline earth metal salt, a quaternary ammonium
salt, a surfactant (a nonionic surfactant, an anionic surfactant, a
cationic surfactant, and an amphoteric surfactant), and an ionic
liquid (a salt existing in the form of liquid at ordinary
temperature and existing in a pair of a cation and an anion).
Specific examples thereof are as described below.
[0310] Alkali metal or alkaline earth metal salt: a salt between
alkali metal (lithium, sodium and potassium) or alkaline earth
metal (magnesium and calcium) and organic acid [monocarboxylic acid
or dicarboxylic acid having 1 to 7 carbon atoms (formic acid,
acetic acid, propionic acid, oxalic acid and succinic acid),
sulfonic acid having 1 to 7 carbon atoms (methanesulfonic acid,
trifluoromethanesulfonic acid and p-toluenesulfonic acid), and
thiocyanic acid]; and a salt between the organic acid and inorganic
acid [halogenated hydroacid (hydrochloric acid and hydrobromic
acid), perchloric acid, sulfuric acid, nitric acid and phosphoric
acid].
[0311] Quaternary ammonium salt: a salt between amidinium
(1-ethyl-3-methylimidazolium) or guanidinium
(2-dimethylamino-1,3,4-trimethylimidazolium) and the organic acid
or inorganic acid.
[0312] Surfactant: sucrose fatty acid ester, sorbitan fatty acid
ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene
fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl
ether, alkyl glycoside, polyoxyethylene alkylphenyl ether, a higher
fatty acid salt (soap), an .alpha.-sulfo fatty acid methyl ester
salt, straight-chain alkylbenzene sulfonate, alkyl sulfate,
alkylether sulfate, (mono)alkyl phosphate, .alpha.-olefin
sulfonate, alkane sulfonate, an alkyltrimethylammonium salt, a
dialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt,
N-methyl-bis-hydroxyethylamine fatty acid ester-hydrochloride, an
alkylamino fatty acid salt, alkyl betaine and alkylamineoxide.
[0313] Ionic liquid: 1,3-ethylmethylimidazolium
bistrifluoromethanesulfonimide, 1,3-ethylmethylimidazorium
tetrafluoroborate, 1-ethylpyridinium
bistrifluoromethanesulfonimide, 1-ethylpyridinium
tetrafluoroborate, 1-ethylpyridinium hexafluorophosphate and
1-methylpyrazolium bistrifluoromethanesulfonimide.
[0314] Further, in the present invention, in order to develop a
maximum of the effect of improving the photochromism, with regard
to a functional group mole ratio of the hydroxyl group and the
thiol group to the isocyanate group and the thioisocyanate group,
an amount of the hydroxyl group and the thiol group per one mol of
the isocyanate group and the thioisocyanate group should be
adjusted to the range from 0.8 to 1.2 mol, particularly preferably
from 0.85 to 1.15 mol, and most preferably from 0.9 to 1.1 mol.
[0315] <Production Method for a Photochromic Optical
Composition>
[0316] When the optical composition according to the present
invention is used as the photochromic optical composition, in
general, in addition to (A) the polyrotaxane, (B) the compound
having two or more groups of at least one kind of group selected
from the isocyanate group and the isothiocyanate group in one
molecule, and (D) the photochromic compound, (C) the
iso(thio)cyanate reactive group-containing compound is preferably
blended therein. For example, the photochromism is desirably
developed by preparing the photochromic optical composition by
melting and kneading each component, preparing the photochromic
cured body by allowing polymerization curing of the resulting
material, and by using the cured body.
[0317] Moreover, when the optical composition according to the
present invention is used as a photochromic coating agent for
improving solubility of a constituent or adjusting a film
thickness, a photochromic coating layer is formed by preparing a
coating liquid by dispersing or dissolving the photochromic optical
composition into an organic solvent, and coating the resulting
coating liquid onto a transparent optical sheet or optical film and
drying the resulting material, thereby enabling to develop the
photochromism. The organic solvent to be used only needs to be
selected appropriately according to use thereof, but in view of the
solubility, ketones such as methyl ethyl ketone and diethyl ketone,
halogens such as methylene chloride and chloroform, aromatic
hydrocarbons such as toluene and xylene, and ethers such as dioxane
and tetrahydropyan are preferably used.
[0318] In the photochromic optical composition, the polymerization
curing is performed in order to prepare the photochromic cured
body. The polymerization curing is performed by performing the
radical polymerization, the ring-opening polymerization, the
anionic polymerization or polycondensation by using heat, or when
necessary, irradiation with active energy rays such as ultraviolet
rays, .alpha.-rays, .beta.-rays and .gamma.-rays or heat, or
simultaneous use of both of heat and irradiation, or the like. More
specifically, an appropriate polymerization means only needs to be
adopted according to a kind of (A) the polyrotaxane, (C) the
iso(thio)cyanate reactive group-containing compound, (E) the resin
modifier, and further (D) the polymerization curing accelerator,
and a form of the photochromic curing body to be formed.
[0319] Upon allowing thermal polymerization of the photochromic
optical composition, a temperature during the polymerization
particularly influences properties of the photochromic cured body
to be obtained. The temperature conditions are influenced by a kind
and an amount of the thermal polymerization initiator or a kind of
the polymerizable monomer, and therefore are unable to be
unequivocally limited. However, in general, a method in which the
polymerization is started at a relatively low temperature, and the
temperature is gradually increased is preferable. A polymerization
time is also different depending on various factors in a manner
similar to the temperature. Therefore, an optimum time according to
these conditions is preferably determined in advance. However, in
general, the conditions are preferably selected in such a manner
that the polymerization is completed in 2 to 48 hours. When a
photochromic laminate sheet is obtained, the polymerization is
preferably performed at a temperature at which a reaction between
the polymerization functional groups progresses, and on the above
occasion, an optimum temperature and the optimum time are
preferably determined so as to achieve an objective molecular
weight.
[0320] Moreover, upon allowing photopolymerization of the
photochromic optical composition, among the polymerization
conditions, ultraviolet intensity particularly influences the
properties of the photochromic cured body to be obtained. The
illuminance conditions are influenced by a kind and an amount of
the photopolymerization initiator and a king of the polymerizable
monomer, and therefore are unable to be unequivocally limited.
However, in general, the conditions are preferably selected so as
to irradiate the composition with ultraviolet rays having a
wavelength of 365 nm and 50 to 500 mW/cm.sup.2 for 0.5 to 5
minutes.
[0321] When the photochromism is developed by the kneading method
by using the polymerization curing described above, the
photochromic cured body shaped into the form of the optical
material such as the lens can be obtained by casting the
photochromic optical composition into a space between the glass
molds kept by an elastomer gasket or spacer, and by performing cast
polymerization by heating the composition in an air oven or
irradiating the composition with the active energy rays such as the
ultraviolet rays according to a kind of the polymerizable monomer
or the polymerization curing agent. According to such a method, an
eyeglass lens provided with the photochromism or the like is
directly obtained.
[0322] When the photochromism is developed by the lamination
method, the coating liquid of the photochromic optical composition
is coated onto a surface of the optical base material such as a
lens base material by spin coating, dipping or the like. When the
photochromic optical composition has high viscosity, the
photochromic optical composition only needs to be appropriately
dissolved into the organic solvent to prepare the coating liquid,
and the coating liquid may be coated thereonto, and dried to remove
the organic solvent. A photochromic layer formed of the
photochromic cured body is formed on the surface of the optical
base material by subsequently performing thermosetting by heating
the composition (coating method). Moreover, upon using a material
having a radical polymerizable group in the resin modifier, the
polymerization curing may be performed by irradiation with
ultraviolet rays, heating or the like in an inert gas such as
nitrogen.
[0323] Moreover, the photochromic layer formed of the photochromic
cured body can be formed on the surface of the optical base
material also by cast polymerization by inner molding, in which an
optical substrate such as the lens base material is arranged by
being faced with the glass mold so that a predetermined airspace is
formed therebetween, the photochromic optical composition is cast
into this airspace, and the polymerization curing is performed by
irradiation with ultraviolet rays, heating or the like in this
state.
[0324] When the photochromic layer is formed on the surface of the
optical base material by the lamination method (the coating method
and the cast polymerization method) as described above, adhesion
between the photochromic layer and the optical base material can
also be improved by applying, onto the surface of the optical base
material in advance, chemical treatment by an alkali solution, an
acid solution or the like, or physical treatment by corona
discharge, plasma discharge, polishing or the like. A transparent
adhesive resin layer can also be obviously provided on the surface
of the optical base material.
[0325] Further, when the photochromism is developed by the binder
method, the photochromic laminate in which the photochromic layer
is applied as an adhesive layer is obtained by preparing a
photochromic sheet by sheet forming using the photochromic optical
composition, interposing the resulting sheet by two transparent
sheets (optical sheets) and performing the polymerization curing
described above.
[0326] In this case, in preparing the photochromic sheet, a means
of coating using the coating liquid in which the photochromic
optical composition is dissolved into the organic solvent can also
be employed.
[0327] The thus prepared photochromic laminate is placed within a
mold, for example, and then a thermoplastic resin (for example,
polycarbonate) for the optical base material such as the lens is
injection-molded thereonto. Thus, the optical base material such as
the lens having a predetermined shape and provided with the
photochromism is obtained. Moreover, this photochromic laminate can
be adhered onto the surface of the optical base material by an
adhesive or the like. Thus, the photochromic lens can also be
obtained.
[0328] The photochromic optical composition described above can
cause development of the photochromism excellent in the color
optical density, the color fading rate or the like, and furthermore
can be effectively used for preparing the optical base material
provided with the photochromism, for example, the photochromic
lens, without reducing the characteristics such as the mechanical
strength.
[0329] Moreover, onto the photochromic layer or the photochromic
cured body formed using the photochromic optical composition,
post-treatment can be applied, according to use thereof, such as
dyeing using a dye such as a disperse dye, preparation of a hard
coat film using a silane coupling agent or a hard coat agent
containing as a main component a sol of silicon, zirconium,
antimony, aluminum, tin and tungsten, formation of a thin film by
vapor deposition of metallic oxide such as SiO.sub.2, TiO.sub.2 and
ZrO.sub.2, and anti-reflection treatment and antistatic treatment
by a thin film by applying an organic polymer thereonto.
EXAMPLES
[0330] Next, the present invention will be described in detail
using Examples and Comparative Examples, but the present invention
is not limited to the present Examples. In the Examples and
Comparative Examples described below, evaluation methods for each
component and photochromic characteristics above are as described
below.
[0331] (A) Preparation of a Polyrotaxane being Characterized in
that a Side Chain Having a Secondary or Tertiary Hydroxyl Group is
Introduced into at Least Part of a Cyclic Molecule (Polyrotaxane
According to Aspect I)
[0332] AI-1: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0333] Hereinafter, a preparation method for a polyrotaxane (AI-1)
will be described below.
[0334] (1-1) Preparation of PEG-COOH:
[0335] As a polymer for forming an axle molecule, straight-chain
polyethylene glycol (PEG) having a weight average molecular weight
of 20,000 was arranged.
[0336] Each component was dissolved into 100 mL of water according
to the formulation described below:
[0337] 10 g of PEG
[0338] 100 mg of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy
radical)
[0339] 1 g of sodium bromide
[0340] To this solution, 5 mL of commercially available sodium
hypochlorite aqueous solution (available chlorine concentration:
5%) was added, and the resulting mixture was stirred at room
temperature for 10 minutes. Then, ethanol was added thereto in the
range of a maximum of up to 5 mL to terminate the reaction. Then,
extraction using 50 mL of methylene chloride was performed, and
then methylene chloride was distilled off, the resulting material
was dissolved into 250 mL of ethanol, and then caused
reprecipitation in 12 hours at a temperature of -4.degree. C., and
PEG-COOH was collected and dried.
[0341] (1-2) Preparation of a Polyrotaxane Having a Primary
Hydroxyl Group in a Side Chain
[0342] Into 50 mL of warm water at 70.degree. C., 3 g of PEG-COOH
prepared as described above and 12 g of .alpha.-cyclodextrin
(.alpha.-CD) were each dissolved, and the resulting each solution
was mixed and shaken up well. Subsequently, reprecipitation was
caused in this mixed solution at a temperature of 4.degree. C. for
12 hours, and a precipitated clathrate complex was freeze-dried and
collected. Then, 0.13 g of adamantanamine was dissolved into 50 mL
of dimethylformamide (DMF) at room temperature, and then the
clathrate complex described above was added thereto, and the
resulting mixture was immediately shaken up well. Subsequently, a
solution in which 0.38 g of BOP reagent
(benzotriazol-1-yl-oxy-tris(dimethylamino)phosphonium
hexafluorophosphate) was dissolved into DMF was further added
thereto, and the resulting mixture was shaken up well. Further, a
solution in which 0.14 mL of diisopropylethylamine was dissolved
into DMF was added thereto, and the resulting mixture was shaken up
well to obtain a slurry-form reagent. The slurry-form reagent
obtained as described above was left to stand at 4.degree. C. for
12 hours. Then, 50 mL of DMF/methanol mixed solvent (volume ratio:
1/1) was added thereto, and mixed, and the resulting mixture was
centrifuged, and a supernatant was disposed of. Further, the
resulting material was washed with the DMF/methanol mixed solution,
and then washed using methanol, and centrifuged to obtain a
deposit. The deposit obtained was dried in vacuum, and then
dissolved into 50 mL of DMSO (dimethylsulfoxide), and a transparent
solution obtained was added dropwise into 700 mL of water to
precipitate a polyrotaxane. The polyrotaxane precipitated was
collected by centrifugal separation, and dried in vacuum. Further,
the resulting polyrotaxane was dissolved into DMSO, precipitated in
water, collected and dried to obtain a purified polyrotaxane. A
clathration amount of .alpha.-CD at this time was 0.25.
[0343] Here, with regard to the clathration amount, the
polyrotaxane was dissolved into DMSO-d.sub.6, and NMR thereof was
measured by .sup.1H-NMR Spectrometer (JNM-LA500, manufactured by
JEOL Ltd.), and the clathration amount was calculated by the
following method.
[0344] Here, X, Y and X/(Y-X) indicate the following meanings.
[0345] X: an integrated value at 4-6 ppm for protons from a
hydroxyl group of cyclodextrin
[0346] Y: an integrated value at 3-4 ppm for protons from methylene
chains of cyclodextrin and PEG
[0347] X/(Y-X): a proton ratio of cyclodextrin to PEG
[0348] First, the clathration amount was calculated by
theoretically calculating in advance X/(Y-X) given at a maximum
clathration amount of 1, and comparing this calculated value with
X/(Y-X) calculated from an analytical value of an actual
compound.
[0349] (1-3) Introduction of a Side Chain into a Polyrotaxane
[0350] Into 50 mL of 1 mol/L NaOH aqueous solution, 500 mg of the
purified polyrotaxane described above was dissolved, 3.83 g (66
mmol) of propylene oxide was added thereto, and under an argon
atmosphere, the resulting mixture was stirred at room temperature
for 12 hours. Subsequently, the polyrotaxane solution described
above was neutralized to be 7 to 8 in pH by using a 1 mol/L HCl
aqueous solution, and the resulting material was dialyzed using a
dialysis tube, and then freeze-dried to obtain a hydroxypropylated
polyrotaxane.
[0351] In addition, a degree of modification to a OH group of the
cyclic molecule by a hydroxypropyl group was 0.5. A mixed liquid in
which 5 g of hydroxypropylated polyrotaxane obtained was dissolved
into 22.5 g of .epsilon.-caprolactone at 80.degree. C. was
prepared. This mixed liquid was stirred at 110.degree. C. for 1
hour while blowing dry nitrogen, and then 0.16 g of 50 wt % xylene
solution of tin(II) 2-ethylhexanoate was added thereto, and the
resulting mixture was stirred at 130.degree. C. for 6 hours. Then,
xylene was added thereto to obtain a xylene solution of a
polycaprolactone-modified polyrotaxane into which a side chain was
introduced, in which a nonvolatile concentration was about 35% by
mass.
[0352] The xylene solution of the polycaprolactone-modified
polyrotaxane prepared as described above was added dropwise into
hexane, and the resulting material was collected and dried to
obtain a polyrotaxane modified with a side chain having a primary
hydroxyl group as a polymerizable functional group (polyrotaxane in
which a molecular weight of the side chain of the polyrotaxane
obtained was about 500 on an average, and according to measurement
by GPC, a weight average molecular weight (Mw) of the polyrotaxane
obtained was 400,000, and a hydroxyl value was 1.35 mmol/g in a
measured value.).
[0353] In addition, in Examples, the weight average molecular
weight of the polyrotaxane was measured using Gel Permeation
Chromatography (GPC) under the following conditions: [0354]
Measuring instrument: Liquid Chromatography (manufactured by Nihon
Waters K.K.) [0355] GPC column: Shodex GPC KF-805 (exclusion limit
molecular weight: 2,000,000) (manufactured by Showa Denko K.K.)
[0356] Flow rate: 1 mL/min [0357] Column temperature: 40.degree. C.
[0358] Sample concentration: 0.5% (w/v) (diluted with DMF) [0359]
Mobile phase solvent: DMF [0360] Standard polystyrene
equivalent
[0361] The hydroxyl value of the polyrotaxane was measured by a
titration method.
[0362] (1-4) Preparation of a Polyrotaxane (AI-1) Having a Tertiary
Hydroxyl Group in a Side Chain
[0363] To 5 g of this polyrotaxane, 15 g of xylene and 0.005 g of
dibutylhydroxytoluene (polymerization inhibitor) were added, and
then under an argon atmosphere, 1.26 g of
2-methyl-2-(trimethylsiloxy)propyl isocyanate was added dropwise
thereto. In addition, 2-methyl-2-(trimethylsiloxy)propyl isocyanate
was added dropwise thereto so as to cause a reaction with a
hydroxyl group of the polyrotaxane at a ratio of 1/1. The resulting
mixture was stirred at 40.degree. C. for 16 hours to obtain a
xylene solution of a polyrotaxane in which a side chain having a
hydroxyl group protected was introduced into an end of
polycaprolactone.
[0364] This xylene solution of the polyrotaxane was added dropwise
into hexane, the resulting material was collected, and then 20 g of
THF was added thereto, and under an argon atmosphere, a TBAF THF
solution (10 mL, 1.0 M) was added thereto, and the resulting
mixture was stirred under heating reflux. After completion of the
reaction, a saturated NH.sub.4Cl aqueous solution was added thereto
to separate a liquid, and an aqueous layer was subjected to
extraction with toluene, and a collected oil layer was dried over
Na.sub.2SO.sub.4. Then, the solvent was removed under reduced
pressure. Thus, a polyrotaxane (AI-1) being characterized in that a
side chain having a tertiary hydroxyl group was introduced into at
least part of the cyclic molecule was able to be obtained. A
molecular weight of the side chain of the polyrotaxane obtained was
about 600 on an average, and according to measurement by GPC, a
weight average molecular weight (Mw) of the polyrotaxane obtained
was 460,000, and the hydroxyl group in the side chain was 100% in
the tertiary hydroxyl group.
[0365] AI-2: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0366] (1-5) Preparation of a Polyrotaxane (AI-2) Having a Tertiary
Hydroxyl Group in a Side Chain:
[0367] A polyrotaxane (AI-2) having a tertiary hydroxyl group in a
side chain was obtained completely in the same manner as in the
(AI-1) except that PEG having a weight average molecular weight of
10,000 was used in place of the PEG having the weight average
molecular weight of 20,000 in (1-1).
[0368] Physical properties of this polyrotaxane (AI-2) were as
described below:
[0369] Clathration amount of .alpha.-CD: 0.25
[0370] Degree of modification with side chain: 0.5
[0371] Molecular weight of side chain: about 600 on an average
[0372] Weight average molecular weight (Mw) of polyrotaxane (GPC):
230,000
[0373] 100% in the tertiary hydroxyl group as the hydroxyl group in
the side chain
[0374] AI-3: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0375] (1-6) Preparation of a Polyrotaxane (AI-3) Having a Tertiary
Hydroxyl Group in a Side Chain:
[0376] A polyrotaxane (AI-3) having a tertiary hydroxyl group in a
side chain was obtained completely in the same manner as in the
(AI-1) except that an amount of .epsilon.-caprolactone in (1-3) was
changed to 125 g.
[0377] Physical properties of this polyrotaxane (AI-3) were as
described below:
[0378] Clathration amount of .alpha.-CD: 0.25
[0379] Degree of modification with side chain: 0.5
[0380] Molecular weight of side chain: about 2,500 on an
average
[0381] Weight average molecular weight (Mw) of polyrotaxane (GPC):
1,900,000
[0382] 100% in the tertiary hydroxyl group as the hydroxyl group in
the side chain
[0383] AI-4: Polyrotaxane Having a Secondary Hydroxyl Group in a
Side Chain
[0384] (1-7) Preparation of a Polyrotaxane (AI-4) Having a
Secondary Hydroxyl Group in a Side Chain:
[0385] A polyrotaxane (AI-4) having a secondary hydroxyl group in a
side chain was obtained completely in the same manner as in the
(AI-1) except that 1.45 g of 2-(t-butyldimethylsiloxy)propyl
isocyanate was used in place of 2-methyl-2-(trimethylsiloxy)propyl
isocyanate in (1-4).
[0386] Physical properties of this polyrotaxane (AI-4) were as
described below:
[0387] Clathration amount of .alpha.-CD: 0.25
[0388] Degree of modification with side chain: 0.5
[0389] Molecular weight of side chain: about 600 on an average
[0390] Weight average molecular weight (Mw) of polyrotaxane (GPC):
460,000
[0391] 100% in the secondary hydroxyl group as the hydroxyl group
in the side chain
[0392] AI-5: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0393] (1-8) Preparation of a Polyrotaxane (AI-5) Having a Tertiary
Hydroxyl Group in a Side Chain:
[0394] A polyrotaxane (AI-5) having a tertiary hydroxyl group in a
side chain was obtained completely in the same manner as in the
(AI-1) except that PEG having a weight average molecular weight of
10,000 was used in place of the PEG having the weight average
molecular weight of 20,000 in (1-1), and 22.5 g of s-caprolactam
was used in place of .epsilon.-caprolactone in (1-3).
[0395] Physical properties of this polyrotaxane (AI-5) were as
described below:
[0396] Clathration amount of .alpha.-CD: 0.25
[0397] Degree of modification with side chain: 0.5
[0398] Molecular weight of side chain: about 600 on an average
[0399] Weight average molecular weight (Mw) of polyrotaxane (GPC):
230,000
[0400] 100% in the tertiary hydroxyl group as the hydroxyl group in
the side chain
[0401] AI-6: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0402] (1-8) Preparation of a Polyrotaxane (AI-6) Having a Tertiary
Hydroxyl Group in a Side Chain:
[0403] A polyrotaxane (AI-6) having a tertiary hydroxyl group in a
side chain was obtained completely in the same manner as in the
(AI-1) except that 22.5 g of .gamma.-valerolactone was used in
place of .epsilon.-caprolactone in (1-3).
[0404] Physical properties of this polyrotaxane (AI-6) were as
described below:
[0405] Clathration amount of .alpha.-CD: 0.25
[0406] Degree of modification with side chain: 0.5
[0407] Molecular weight of side chain: about 500 on an average
[0408] Weight average molecular weight (Mw) of polyrotaxane (GPC):
400,000
[0409] 100% in the tertiary hydroxyl group as the hydroxyl group in
the side chain
[0410] AI-7: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0411] (1-9) Preparation of a Polyrotaxane (AI-7) Having a Tertiary
Hydroxyl Group in a Side Chain:
[0412] A polyrotaxane (AI-7) having a tertiary hydroxyl group in a
side chain was obtained in the same manner as in the preparation
method for the (AI-1) except that PEG having a weight average
molecular weight of 90,000 was used in place of the PEG having the
weight average molecular weight of 20,000 in (1-1), and an amount
of .epsilon.-caprolactone in (1-3) was changed to 12.5 g.
[0413] Physical properties of this polyrotaxane (AI-7) were as
described below:
[0414] Clathration amount of .alpha.-CD: 0.25
[0415] Degree of modification with side chain: 0.5
[0416] Molecular weight of side chain: about 400 on an average
[0417] Weight average molecular weight (Mw) of polyrotaxane (GPC):
1,500,000
[0418] 100% in the tertiary hydroxyl group as the hydroxyl group in
the side chain
[0419] AI-8: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0420] (1-10) Preparation of a Polyrotaxane (AI-8) Having a
Tertiary Hydroxyl Group in a Side Chain:
[0421] A polyrotaxane (AI-8) having a tertiary hydroxyl group in a
side chain was obtained in the same manner as in the preparation
method for the (AI-1) except that an amount of
2-methyl-2-(trimethylsiloxy)propyl isocyanate was changed to 0.63 g
in (1-4).
[0422] Clathration amount of .alpha.-CD: 0.25
[0423] Degree of modification with side chain: 0.5
[0424] Molecular weight of side chain: about 550 on an average
[0425] Weight average molecular weight (Mw) of polyrotaxane (GPC):
430,000
[0426] 50% in the tertiary hydroxyl group and 50% in the primary
hydroxyl group as the hydroxyl group in the side chain
[0427] AI-9: Polyrotaxane Having a Tertiary Hydroxyl Group in a
Side Chain
[0428] (1-11) Preparation of a Polyrotaxane (AI-9) Having a
Tertiary Hydroxyl Group in a Side Chain:
[0429] A polyrotaxane (AI-9) having a tertiary hydroxyl group in a
side chain was obtained in the same manner as in the preparation
method in preparation method for the (AI-1) except that an amount
of 2-methyl-2-(trimethylsiloxy)propyl isocyanate was changed to
1.01 g in (1-4)
[0430] Clathration amount of .alpha.-CD: 0.25
[0431] Degree of modification with side chain: 0.5
[0432] Molecular weight of side chain: about 600 on an average
[0433] Weight average molecular weight (Mw) of polyrotaxane (GPC):
450,000
[0434] 80% in the tertiary hydroxyl group and 20% in the primary
hydroxyl group as the hydroxyl group in the side chain
[0435] The features of the (A) polyrotaxanes (AI-1) to (AI-9)
prepared as described above were summarized in Table 1.
[Table 1]
TABLE-US-00001 [0436] TABLE 1 (A) Polyrotaxane Weight Molecular
Clathration Degree of average Straight- weight of amount of
modification Molecular molecular chain straight cyclic Side-chain
of side weight of weight of molecule chain Cyclic molecule molecule
molecule chain Shape of side chain end side chain polyrotaxane AI-1
PEG 20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5
Tertiary hydroxyl group 600 460,000 100% AI-2 PEG 10,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 Tertiary
hydroxyl group 600 230,000 100% AI-3 PEG 20,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 Tertiary
hydroxyl group 2,500 1,900,000 100% AI-4 PEG 20,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 Secondary
hydroxyl group 600 460,000 100% AI-5 PEG 10,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactam 0.5 Tertiary
hydroxyl group 600 230,000 100% AI-6 PEG 20,000
.alpha.-Cyclodextrin 0.25 .gamma.-Valerolactone 0.5 Tertiary
hydroxyl group 500 400,000 100% AI-7 PEG 90,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 Tertiary
hydroxyl group 400 1,500,000 100% AI-8 PEG 20,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 Tertiary
hydroxyl group/ 550 430,000 Primary hydroxyl group 50%/50% AI-9 PEG
20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5
Tertiary hydroxyl group/ 600 450,000 Primary hydroxyl group
80%/20%
[0437] (A) Preparation of a Polyrotaxane being Characterized in
that a Side Chain Having a Hydroxyl Group a pKa of which is 6 or
More and Less than 14 is Introduced into at Least Part of a Cyclic
Molecule (Polyrotaxane According to Aspect II):
[0438] AII-1: Polyrotaxane Having a Hydroxyl Group a pKa of which
is 10 in a Side Chain
[0439] A preparation method for a polyrotaxane (AII-1) will be
described below.
[0440] The operation up to "(1-3) Introduction of a side chain into
a polyrotaxane" described above was performed in the same manner as
in the preparation method for the polyrotaxane (AI-1).
[0441] A polyrotaxane modified with a side chain having a primary
hydroxyl group as a polymerizable functional group obtained in
"(1-3) Introduction of a side chain to a polyrotaxane" being the
preparation method for the polyrotaxane (AI-1) (polyrotaxane in
which a molecular weight of the side chain of the polyrotaxane
obtained was about 500 on an average, and according to measurement
by GPC, a weight average molecular weight (Mw) of the polyrotaxane
obtained was 400,000, and a hydroxyl value was 1.35 mmol/g in a
measured value.) was a polyrotaxane modified with a side chain
having a primary hydroxyl group a pKa of which is 15.5 (H-A in the
formula (2): methanol).
[0442] (1-4) Preparation of a Polyrotaxane Having a Hydroxyl Group
a pKa of which is 10 in a Side Chain
[0443] To 5 g of this polyrotaxane, 15 g of xylene and 0.005 g of
dibutylhydroxytoluene (polymerization inhibitor) were added, and
then under an argon atmosphere, 1.59 g of
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was added
dropwise thereto, in which
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was added
dropwise thereto to be equimolar with the mole of the hydroxyl
group in the polyrotaxane. The resulting mixture was stirred at
40.degree. C. for 16 hours, and overall consumption of the raw
materials was confirmed to obtain a xylene solution of a
polyrotaxane in which a side chain having a hydroxyl group
protected was introduced into an end of polycaprolactone.
[0444] This xylene solution of the polyrotaxane was added dropwise
into hexane, the resulting material was collected, and then 20 g of
THF was added thereto, and under an argon atmosphere, a
tetra-n-butylammonium fluoride (TBAF) THF solution (10 mL, 1.0 M)
was added thereto, and the resulting mixture was stirred under
heating reflux. After completion of the reaction, a saturated
NH.sub.4Cl aqueous solution was added thereto to separate a liquid,
and an aqueous layer was subjected to extraction with toluene, and
a collected oil layer was dried over Na.sub.2SO.sub.4. Then, the
solvent was removed under reduced pressure, and a polyrotaxane in
which a side chain having a hydroxyl group a pKa of which is 10 in
a side chain was introduced into at least part of a cyclic molecule
was able to be obtained (H-A in the formula (2): phenol). In
addition, the pKa is expressed in terms of a value in water, and
the pKa described in (a) "Handbook of Chemistry edited by the
Chemical Society of Japan" (3.sup.rd edition, published on Jun. 25,
1984, published by Maruzen Co., Ltd.). With regard to the pKa not
described in (a), a value of pKa can be obtained by carrying out
measurement according to the method described in (b) The Journal of
Physical Chemistry, vol. 68, number 6, page 1560 (1964). A
molecular weight of the side chain of the polyrotaxane obtained was
about 650 on an average, and according to measurement by GPC, a
weight average molecular weight of the polyrotaxane obtained was
477,000. Moreover, with regard to the hydroxyl group at the end,
from overall consumption of
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene, all the
hydroxyl groups of the polyrotaxane obtained in (1-3) were
substituted.
[0445] AII-2: Preparation of a Polyrotaxane Having a Hydroxyl Group
a pKa of which is 10 in a Side Chain
[0446] (1-5) Preparation of a Polyrotaxane (AII-2) Having a
Hydroxyl Group a pKa of which is 10 in a Side Chain:
[0447] A polyrotaxane (AII-2) having a hydroxyl group a pKa of
which is 10 in a side chain was obtained completely in the same
manner as in the (AII-1) except that PEG having a weight average
molecular weight of 10,000 was used in place of the PEG having the
weight average molecular weight of 20,000 in (1-1).
[0448] Physical properties of this polyrotaxane (AII-2) were as
described below:
[0449] Clathration amount of .alpha.-CD: 0.25
[0450] Degree of modification with side chain: 0.5
[0451] Molecular weight of side chain: about 650 on an average
[0452] Weight average molecular weight (Mw) of polyrotaxane (GPC):
239,000
[0453] 100% in the hydroxyl group the pKa of which is 10 in the
side chain (H-A in the formula (2): phenol)
[0454] AII-3: Preparation of a Polyrotaxane Having a Hydroxyl Group
a pKa of which is 10 in a Side Chain
[0455] (1-6) Preparation of a Polyrotaxane (AII-3) Having a
Hydroxyl Group a pKa of which is 10 in a Side Chain:
[0456] A polyrotaxane (AII-3) having a hydroxyl group a pKa of
which is 10 in a side chain was prepared completely in the same
manner as in the (AII-1) except that an amount of
.epsilon.-caprolactone in (1-3) was changed to 125 g.
[0457] Physical properties of this polyrotaxane (AII-3) were as
described below:
[0458] Clathration amount of .alpha.-CD: 0.25
[0459] Degree of modification with side chain: 0.5
[0460] Molecular weight of side chain: about 2,500 on an
average
[0461] Weight average molecular weight (Mw) of polyrotaxane (GPC):
1,900,000
[0462] 100% in the hydroxyl group the pKa of which is 10 in the
side chain (H-A in the formula (2): phenol)
[0463] AII-4: Polyrotaxane Having a Hydroxyl Group a pKa of which
is 9.3 in a Side Chain
[0464] (1-7) Preparation of a Polyrotaxane (AII-4) Having a
Hydroxyl Group a pKa of which is 9.3 in a Side Chain:
[0465] A saturated solution of 140 mL of dichloromethane and 140 mL
of NaHCO.sub.3 was added to 1.94 g of
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine
at room temperature, and then the resulting mixture was cooled to
0.degree. C. while stirring the mixture, and then stirring was
stopped. Then, the liquid was separated into two layers, and then
1.35 g of triphosgene dissolved in a dichloromethane solution (15
mL) was added to an organic layer with a syringe, and the resulting
mixture was immediately stirred again for 30 minutes. Then, the
mixture was separated into an aqueous layer and an organic layer,
the aqueous layer was subjected to liquid separation and extraction
with dichloromethane again, and then a moisture was removed from
the organic layer with Na.sub.2SO.sub.4, and the resulting mixture
was concentrated to be taken as
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propane
isocyanate. Then, to
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propane
isocyanate concentrated, under an argon atmosphere, 5 g of the
polyrotaxane synthesized in (1-3), 15 g of xylene and 0.005 g of
dibutylhydroxytoluene (polymerization inhibitor) were added, and
then under the argon atmosphere, the resulting mixture was stirred
at 40.degree. C. for 16 hours. Completion of the reaction was
confirmed by overall consumption of
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propane
isocyanate to obtain a xylene solution of a polyrotaxane in which a
side chain having a hydroxyl group protected was introduced into an
end of the polycaprolactone.
[0466] This xylene solution of the polyrotaxane was added dropwise
into hexane, and the resulting material was collected, and then a
mixed solution of 18 g of THF and 2 g of MeOH was added thereto.
Further, 0.07 g of 10% Pd/C was added thereto at room temperature,
and then an atmosphere was replaced by hydrogen, the resulting
mixture was stirred at 60.degree. C. for 1.5 hours, and a
polyrotaxane being characterized in that a side chain having a
hydroxyl group a pKa of which is 9.3 was introduced thereinto was
able to be obtained (H-A in the formula (2):
(CF.sub.3).sub.2-CH.sub.2--OH). A molecular weight of the side
chain of the polyrotaxane obtained was about 700 on an average, and
according to measurement by GPC, a weight average molecular weight
(Mw) of the polyrotaxane obtained was 470,000. Moreover, all the
hydroxyl groups at the end were substituted because all of
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene were
consumed.
[0467] Physical properties of this polyrotaxane (AII-4) were as
described below:
[0468] Clathration amount of .alpha.-CD: 0.25
[0469] Degree of modification with side chain: 0.5
[0470] Molecular weight of side chain: about 700 on an average
[0471] Weight average molecular weight (Mw) of polyrotaxane (GPC):
500,000
[0472] 100% in the hydroxyl group the pKa of which is 9.3 in the
side chain (H-A in the formula (2):
(CF.sub.3).sub.2--CH.sub.2--OH)
[0473] AII-5: Preparation of a Polyrotaxane Having a Hydroxyl Group
a pKa of which is 12.5 in a Side Chain
[0474] (1-8) Preparation of a Polyrotaxane (A-5) Having a Hydroxyl
Group a pKa of which is 12.5 in a Side Chain:
[0475] A polyrotaxane (A-5) having a hydroxyl group a pKa of which
is 12.5 in a side chain was obtained in the same manner as in the
preparation method for the (AII-4) except that 1.58 g of
4,4,4-trifluoro-3-(phenylmethoxy)-1-butaneamine was applied in
place of
3,3,3-trifluoro-2-(phenylmethoxy)-2-(trifluoromethyl)-1-propaneamine
in (1-7) (H-A in the formula (2): CF.sub.3--CH.sub.2--OH).
[0476] Physical properties of this polyrotaxane (AII-5) were as
described below:
[0477] Clathration amount of .alpha.-CD: 0.25
[0478] Degree of modification with side chain: 0.5
[0479] Molecular weight of side chain: about 650 on an average
[0480] Weight average molecular weight (Mw) of polyrotaxane (GPC):
477,000
[0481] 100% in the hydroxyl group the pKa of which is about 12.5 in
the side chain (H-A in the formula (2): CF.sub.3--CH.sub.2--OH)
[0482] AII-6: Polyrotaxane Having a Hydroxyl Group a pKa of which
is 10 in a Side Chain
[0483] (1-9) Preparation of a Polyrotaxane Having a Hydroxyl Group
a pKa of which is 10 in a Side Chain:
[0484] A polyrotaxane (AII-6) having a hydroxyl group a pKa of
which is 10 in a side chain was obtained in the same manner as in
the preparation method for the (AII-1) except that PEG having a
molecular weight of 90,000 was used in place of the PEG having the
weight average molecular weight of 20,000 in (1-1), and an amount
of .epsilon.-caprolactone in (1-3) was changed to 10.5 g.
[0485] Physical properties of this polyrotaxane (AII-6) were as
described below:
[0486] Clathration amount of .alpha.-CD: 0.25
[0487] Degree of modification with side chain: 0.5
[0488] Molecular weight of side chain: about 400 on an average
[0489] Weight average molecular weight (Mw) of polyrotaxane (GPC):
1,500,000
[0490] 100% in the hydroxyl group the pKa of which is 10 in the
side chain (H-A in the formula (2): phenol)
[0491] AII-7: Polyrotaxane Having a Hydroxyl Group a pKa of which
is 10 in a Side Chain
[0492] (1-10) Preparation of a Polyrotaxane (AII-7) Having a
Hydroxyl Group a pKa of which is 10 in a Side Chain:
[0493] A polyrotaxane (AII-7) having a hydroxyl group a pKa of
which is 10 in a side chain was obtained in the same manner as in
the preparation method for the (AII-1) except that an amount of
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was changed
to 0.80 g in (1-4).
[0494] Physical properties of this polyrotaxane (AII-7) were as
described below:
[0495] Clathration amount of .alpha.-CD: 0.25
[0496] Degree of modification with side chain: 0.5
[0497] Molecular weight of side chain: about 600 on an average
[0498] Weight average molecular weight (Mw) of polyrotaxane (GPC):
439,000
[0499] 50% in the hydroxyl group the pKa of which is 10 in the side
chain (H-A in the formula (2): phenol) and 50% in the hydroxyl
group the pKa of which is 15.5 in the side chain (H-A in the
formula (2): methanol)
[0500] AII-8: Polyrotaxane Having a Hydroxyl Group a pKa of which
is 10 in a Side Chain
[0501] (1-11) Preparation of a Polyrotaxane (AII-8) Having a
Hydroxyl Group a pKa of which is 10 in a Side Chain:
[0502] A polyrotaxane (AII-8) having a hydroxyl group a pKa of
which is 10 in a side chain was obtained in the same manner as in
the preparation method for the (AII-1) except that an amount of
1-(2-isocyanatoethyl)-4-[(trimethylsilyl)oxy]-benzene was changed
to 1.43 g in (1-4).
[0503] Physical properties of this polyrotaxane (AII-8) were as
described below:
[0504] Clathration amount of .alpha.-CD: 0.25
[0505] Degree of modification with side chain: 0.5
[0506] Molecular weight of side chain: about 650 on an average
[0507] Weight average molecular weight (Mw) of polyrotaxane (GPC):
470,000
[0508] 90% in the hydroxyl group the pKa of which is 10 in the side
chain (H-A in the formula (2): phenol) and 10% in the hydroxyl
group the pKa of which is 15.5 in the side chain (H-A in the
formula (2): methanol)
[0509] Features of the (A) polyrotaxanes (AII-1) to (AII-8)
prepared as described above were summarized in Table 2.
TABLE-US-00002 TABLE 2 (A) Polyrotaxane Weight Molecular
Clathration Degree of average Straight- weight of amount of
modification Molecular molecular chain straight cyclic Side-chain
of side weight of weight of molecule chain Cyclic molecule molecule
molecule chain Shape of side chain end side chain polyrotaxane
AII-1 PEG 20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone
0.5 pKa = 10 650 477,000 100% AII-2 PEG 10,000 .alpha.-Cyclodextrin
0.25 .epsilon.-Caprolactone 0.5 pKa = 10 650 239,000 100% AII-3 PEG
20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 pKa =
10 2,500 1,900,000 100% AII-4 PEG 20,000 .alpha.-Cyclodextrin 0.25
.epsilon.-Caprolactone 0.5 pKa = 9.3 700 500,000 100% AII-5 PEG
20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 pKa =
12.5 650 477,000 100% AII-6 PEG 90,000 .alpha.-Cyclodextrin 0.25
.epsilon.-Caprolactone 0.5 pKa = 10 400 1,500,000 100% AII-7 PEG
20,000 .alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 pKa =
10/pKa = 15.5 600 439,000 50%/50% AII-8 PEG 20,000
.alpha.-Cyclodextrin 0.25 .epsilon.-Caprolactone 0.5 pKa = 10/pKa =
15.5 650 470,000 90%/10%
[0510] (B) Compound Having Two or More Groups of at Least One Kind
of Group Selected from an Isocyanate Group and an Isothiocyanate
Group in One Molecule:
[0511] XDI: m-xylene diisocyanate
[0512] NBDI: (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene
diisocyanate
[0513] HXDI: 1,3-bis(isocyanatomethyl)cyclohexane
[0514] (C) Iso(Thio)Cyanate Reactive Group-Containing Compound
[0515] (C-1) Poly(Thi)Ol Compound Having Two or More Groups of at
Least One Kind of Group Selected from a Hydroxyl Group and a Thiol
Group in One Molecule
[0516] PL1: DURANOL, manufactured by Asahi Kasei Chemicals Co.,
Ltd. (polycarbonate diol, number average molecular weight: 500)
[0517] TMP: trimethylolpropane
[0518] PNT-40: pentaerythritol polyoxyethylene ether
(tetrafunctional polyol, manufactured by Nippon Nyukazai Co.,
Ltd.)
[0519] Polythiol:
[0520] PEMP: pentaerythritol tetrakis(3-mercaptopropionate)
[0521] DPMP: dipentaerythritol hexakis(3-mercaptopropionate)
[0522] EGMP-4: tetraethylene glycol bis(3-mercaptopropionate)
[0523] PRX: polyrotaxane having a primary hydroxyl group in a side
chain
[0524] A polyrotaxane having a primary hydroxyl group in a side
chain obtained in "(1-3) Introduction of a side chain into a
polyrotaxane" in the process of producing AI-1 (H-A in the formula
(2): methanol)
[0525] Degree of modification with side chain: 0.5
[0526] Molecular weight of side chain: about 500 on an average
[0527] Weight average molecular weight (Mw) of polyrotaxane (GPC):
400,000
[0528] 100% in the primary hydroxyl group as the hydroxyl group in
the side chain (H-A in the formula (2): methanol)
[0529] (C-2) Mono(Thi)Ol Compound Having One Hydroxyl Group or One
Thiol Group in One Molecule:
[0530] PGME10: polyethylene glycol monooleyl ether (n.apprxeq.10,
Mw.apprxeq.668)
[0531] 3-MBMA: 3-methoxybutyl thioglycolate
[0532] 1-DT: dodecanethiol
[0533] Photochromic Compound (D): PC1:
##STR00014##
[0534] (F) Polymerization Curing Accelerator:
[0535] Reaction catalyst for urethane or urea:
[0536] DBTD: dibutyltin dilaurate
[0537] (G) Internal Mold Release Agent:
[0538] DBP: di-n-butyltin PA2EE: phosphoric acid 2-ethylhexyl
(mono- and di-mixture)
[0539] Other Blends
[0540] Stabilizer:
[0541] HALS: bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate
(molecular weight: 508)
Example I-1
[0542] A homogeneous liquid (optical composition) was prepared by
mixing each component according to the following formulation. Each
blending amount is shown in Table 3.
Formulation:
[0543] (A) Polyrotaxane: 8 parts by mass of AI-1
[0544] (B) Polyisocyanate compound: 47 parts by mass of NBDI
[0545] (C) Poly(thi)ol compound: 20 parts by mass of PL1, 16 parts
by mass of TMP, [0546] Mono(thi)ol compound: 9 parts by mass of
PGME10
[0547] (D) Photochromic compound: 0.04 part by mass of PC1
[0548] (H) Internal mold release agent: 0.3 part by mass of PA2EE
(based on a total amount of the mixture)
[0549] (Other blends): 0.1 part by mass of HALS
[0550] A photochromic cured body was obtained according to a
kneading method by using the optical composition. A polymerization
method is described below.
[0551] More specifically, the homogeneous liquid was sufficiently
defoamed, and then cast into two kinds of mold forms, including a
glass mold designed to be 2 mm and 10 mm in a thickness of a cured
body obtained, and a casting mold formed of a gasket composed of an
ethylene-vinyl acetate copolymer. Subsequently, while a temperature
was gradually raised from 30.degree. C. to 100.degree. C., the
composition was cured in 15 hours. After completion of
polymerization, a photochromic cured body was removed from the
glass mold of the form to obtain the photochromic cured bodies
having a thickness of 2 mm and a thickness of 10 mm. Photochromic
characteristics, Rockwell hardness L scale (HL), moldability and
cloudiness of the photochromic cured body (2 mm-thick) obtained
were evaluated. As a result, a maximum absorption wavelength was
577 nm, color optical density was 0.89, a color fading rate was 52
seconds, Rockwell hardness L scale (HL) was 77, moldability-1 was
1, and cloudiness-1 was 1. Moreover, moldability and cloudiness of
the photochromic cured body (10 mm-thick) were evaluated. As a
result, moldability-2 was 1, and cloudiness-2 was 1. In addition,
the maximum absorption wavelength, the color optical density, the
color fading rate, the Rockwell hardness L scale, the moldability-1
and the moldability-2, and the cloudiness-1 and the cloudiness-2
were evaluated according to the methods described below.
[Evaluation Items]
[0552] (1) Maximum absorption wavelength (.lamda.max): A maximum
absorption wavelength after color development, which was determined
using Spectrophotometer (Instantaneous Multi Channel Photo Detector
MCPD1000), manufactured by Otsuka Electronics Co., Ltd., after a
photochromic cured body (2 mm-thick) obtained was applied as a
sample, and irradiated with light having a beam intensity of 2.4
mW/cm.sup.2 at 365 nm and 24 .mu.W/cm.sup.2 at 245 nm on a surface
of the cured body at 20.degree. C..+-.1.degree. C. for 120 seconds
through Aero Mass Filter (manufactured by Corning Corporation) by
using Xenon Lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu
Photonics K.K. to develop color. The maximum absorption wavelength
relates to a color tone during color development.
[0553] (2) Color optical density { (120)- (0)}: A difference
between, at the maximum absorption wavelength, an absorbance (
(120)) after irradiation with light for 120 seconds and an
absorbance ( (0)) before irradiation with light. As this value is
higher, the photochromism may be reasonably referred to as being
superb. Moreover, when the color was developed outdoors, a coloring
tone was visually evaluated.
[0554] (3) Color fading rate [t1/2(sec)]: A time required for
reduction to one half of { (120)- (0)} in the absorbance at the
maximum absorption wavelength of the sample upon irradiating the
sample with light for 120 seconds and then stopping the irradiation
with light. As this time is shorter, the photochromism may be
reasonably referred to as being superb.
[0555] (4) Rockwell hardness L scale (HL): Rockwell harness L scale
of the photochromic cured body (2 mm-thick) was measured using
Akashi Rockwell Hardness Tester (Model: AR-10) after the cured body
(2 mm-thick) was kept at 25.degree. C. for one day in a room.
[0556] (5) Moldability-1:
[0557] Optical strain of the photochromic cured body (2 mm-thick)
was visually observed. Evaluation criteria are as described
below.
[0558] 1: Free from optical strain
[0559] 2: Optical strain partially observable in a half part or
less of a lens
[0560] 3: Optical strain observable wholly in a lens
[0561] (6) Cloudiness-1:
[0562] Cloudiness of the photochromic cured body (2 mm-thick) was
visually evaluated. Evaluation criteria are as described below.
[0563] 1: Level having no problem as a product, and free from
cloudiness or almost invisible
[0564] 2: Level having no problem as a product, but somewhat
cloudy
[0565] 3: Level having no problem as a product, but stronger in
cloudiness than the level 2
[0566] 4: Cloudy, and unusable as a product
[0567] (7) Moldability-2:
[0568] Optical strain of the cured body (10 mm-thick) was evaluated
using a high-pressure mercury lamp. More specifically, a surface of
the cured body (10 mm-thick) was irradiated with light from the
high-pressure mercury lamp, and moldability was evaluated by
visually observing a projection thereof. Evaluation criteria are as
described below.
[0569] 1: Free from optical strain
[0570] 2: Optical strain partially observable in a half part or
less of a lens
[0571] 3: Optical strain observable in a half part or more of a
lens
[0572] 4: Optical strain observable wholly in a lens
[0573] (8) Cloudiness-2:
[0574] Cloudiness of the cured body (10 mm-thick) was evaluated
using a high-pressure mercury lamp. More specifically, a side
surface of the cured body (10 mm-thick) was irradiated with light
from the high-pressure mercury lamp, and a degree of cloudiness was
evaluated by visually observing the cured body (10 mm-thick) from
the surface. Evaluation criteria are as described below.
[0575] 1: Free from cloudiness or almost invisible
[0576] 2: Level having no problem as a product, but somewhat
cloudy
[0577] 3: Level having no problem as a product, but stronger in
cloudiness than the level 2
[0578] 4: Cloudy, and unusable as a product
Example 1-2 to I-11, Comparative Examples I-1 to I-3
[0579] A photochromic cured body was prepared in the same manner as
in Example I-1 except that a photochromic optical composition
having a formulation shown in Table 3 was used, and the resulting
material was evaluated. The results were shown in Table 4.
Moreover, the photochromic compound (D) component was not added
thereto in Example I-11 and Comparative Example 1-3, and therefore
the photochromic characteristics were not measured. Moreover,
moldability-1 and cloudiness-1 were evaluated with reference to
Patent literature 8.
TABLE-US-00003 TABLE 3 (A) Component (B) Component (parts by (parts
by (C) Component (D) (F) (G) Other No. mass) mass) (parts by mass)
Component Component Component blends Example I-1 AI-1 (8) NBDI (47)
PL1 (20)/TMP (16)/PGME10 PC1 (0.04) -- PA2EE (0.3) HALS (9) (0.1)
Example I-2 AI-2 (10) NBDI (36) PNT-40 (19)/PL1 (24)/ PC1 (0.04) --
PA2EE (0.3) -- PGME10 (11) Example I-3 AI-5 (12) NBDI (52) PL1
(16)/TMP (20) PC1 (0.04) -- PA2EE (0.3) HALS (0.1) Example I-4 AI-3
(16) XDI (37) PEMP (47) PC1 (0.04) DBTD DBP (0.3) -- (0.1) Example
I-5 AI-4 (5) XDI (40) DPMP (50)/3-MBMA (5) PC1 (0.04) DBTD DBP
(0.3) -- (0.1) Example I-6 AI-6 (2) XDI (39) DPMP (48)/1-DT (11)
PC1 (0.04) DBTD DBP (0.3) HALS (0.1) (0.1) Example I-7 AI-7 (5) XDI
(40) PEMP (46)/EGMP-4 (9) PC1 (0.04) DBTD DBP (0.3) -- (0.1)
Example I-8 AI-6 (5) XDI (39) DPMP (46)/EGMP-4 (5)/3- PC1 (0.04)
DBTD DBP (0.3) HALS MBMA (5) (0.1) (0.1) Example I-9 AI-8 (9) XDI
(39) PEMP (43)/1-DT (9) PC1 (0.04) DBTD -- -- (0.1) Example I- AI-9
(7) NBDI (55) PL1 (17)/TMP (21) PC1 (0.04) -- PA2EE (0.3) -- 10
Example I- AI-1 (6) XDI (40) DPMP (54) -- DBTD DBP (0.3) -- 11
(0.1) Comparative -- NBDI (47) PL1 (20)/TMP (16)/PGME10 PC1 (0.04)
-- PA2EE (0.3) -- Example I-1 (9)/PRX (8) Comparative -- XDI (39)
DPMP (46)/EGMP-4 (5)/3- PC1 (0.04) DBTD DBP (0.3) HALS Example I-2
MBMA (5)/PRX (5) (0.1) (0.1) Comparative -- XDI (36) DPMP (50)/PRX
(14) -- DBTD DBP (0.3) HALS Example I-3 (0.1) (0.1)
TABLE-US-00004 TABLE 4 Maximum absorption Color wavelength Color
optical fading rate No. (.lamda.max) density (second) HL
Moldability-1 Cloudiness-1 Moldability-2 Cloudiness-2 Example I-1
577 0.89 52 77 1 1 1 1 Example I-2 578 0.92 48 77 1 1 1 1 Example
I-3 579 0.78 55 95 1 1 2 1 Example I-4 585 0.64 53 99 1 1 2 2
Example I-5 584 0.79 51 76 1 1 1 1 Example I-6 584 0.57 55 88 1 1 1
1 Example I-7 590 0.58 72 82 1 1 2 1 Example I-8 585 0.88 50 75 1 1
1 1 Example I-9 584 0.60 52 84 1 1 1 2 Example I-10 579 0.74 56 96
1 1 2 1 Example I-11 -- -- -- 110 1 1 1 1 Comparative 576 0.90 48
75 1 1 4 1 Example I-1 Comparative 584 0.88 48 73 1 1 3 3 Example
I-2 Comparative -- -- -- 85 1 2 3 4 Example I-3
Example II-1
[0580] A homogeneous liquid (optical composition) was prepared by
mixing each component according to the following formulation. Each
blending amount is shown in Table 5.
Formulation:
[0581] (A) Polyrotaxane: 8 parts by mass of AII-1
[0582] (B) Polyisocyanate compound: 47 parts by mass of NBDI
[0583] (C) Poly(thi)ol compound: 22 parts by mass of PL1, 16 parts
by mass of TMP, [0584] Mono(thi)ol compound: 7 parts by mass of
PGME10
[0585] (D) Photochromic compound: 0.04 part by mass of PC1
[0586] (H) Internal mold release agent: 0.3 part by mass of
PA2EE
[0587] (Other blends): 0.1 part by mass of HALS
[0588] A photochromic cured body was obtained according to a
kneading method by using the optical composition. A polymerization
method will be described below.
[0589] More specifically, the homogeneous liquid was sufficiently
defoamed, and then cast into two kinds of mold forms, including a
glass mold designed to be 2 mm and 10 mm in a thickness of a cured
body obtained, and a casting mold formed of a gasket composed of an
ethylene-vinyl acetate copolymer. Next, while a temperature was
gradually raised from 30.degree. C. to 100.degree. C., the
composition was cured in 15 hours. After completion of
polymerization, a photochromic cured body was removed from the
glass mold of the form to obtain the photochromic cured bodies
having a thickness of 2 mm and a thickness of 10 mm. Photochromic
characteristics, Rockwell hardness L scale (HL), moldability and
cloudiness of the photochromic cured body (2 mm-thick) obtained
were evaluated. As a result, a maximum absorption wavelength was
579 nm, color optical density was 0.90, a color fading rate was 54
seconds, Rockwell hardness L scale (HL) was 80, moldability-1 was 1
and cloudiness-1 was 1. Moreover, moldability and cloudiness of the
photochromic cured body (10 mm-thick) were evaluated. As a result,
moldability-2 was 1 and cloudiness-2 was 1. In addition, the
maximum absorption wavelength, the color optical density, the color
fading rate, the Rockwell hardness L scale, the moldability-1 and
the moldability-2, and the cloudiness-1 and the cloudiness-2 were
evaluated according to the methods described above.
Examples II-2 to 11-8, Comparative Examples II-1 to II-3
[0590] A photochromic cured body was prepared in the same manner as
in Example II-1 except that a photochromic optical composition
having a formulation shown in Table 5 was used, and the resulting
material was evaluated. The results were shown in Table 6.
Moreover, the photochromic compound (D) component was not added
thereto in Example II-7 and Comparative Example 11-3, and therefore
the photochromic characteristics were not measured. Moreover,
moldability-1 and cloudiness-1 were evaluated with reference to
Patent literature 8.
[0591] In addition, experiments in Comparative Examples I-1 to I-3
are the same experiments in Comparative Examples II-1 to 11-3,
respectively.
TABLE-US-00005 TABLE 5 (A) Component (B) Component (C) Component
(D) (F) (G) Other No. (parts by mass) (parts by mass) (parts by
mass) Component Component Component blends Example II-1 AII-1 (8)
NBDI (47) PL1 (22)/TMP (16)/PGME10 (7) PC1 (0.04) -- PA2EE (0.3)
HALS (0.1) Example II-2 AII-2 (5) NBDI (38) PNT-40 (20)/PL1
(25)/PGME10 PC1 (0.04) -- PA2EE (0.3) -- (12) Example II-3 AII-3
(8) XDI (40) PEMP (48)/3-MBMA (4) PC1 (0.04) DBTD DBP (0.3) HALS
(0.1) (0.1) Example II-4 AII-4 (5) XDI (40) DPMP (45)/PEMP (10) PC1
(0.04) DBTD DBP (0.3) -- (0.1) Example II-5 AII-5 (12) HXDI (49)
PL1 (20)/TMP (19) PC1 (0.04) -- PA2EE (0.3) HALS (0.1) Example II-6
AII-6 (8) XDI (39) PEMP (48)/EGMP-4 (5) PC1 (0.04) DBTD DBP (0.3)
HALS (0.1) (0.1) Example II-7 AII-7 (5) XDI (42) PEMP (53) -- DBTD
DBP (0.3) -- (0.1) Example II-8 AII-8 (4) XDI (40) DPMP (23)/EGMP-4
(7)/PEMP PC1 (0.04) DBTD DBP (0.3) HALS (24)/3-MBMA (2) (0.1) (0.1)
Comparative -- NBDI (47) PL1 (20)/TMP (16)/PGME10 (9)/ PC1 (0.04)
-- PA2EE (0.3) -- Example II-1 PRX (8) Comparative -- XDI (39) DPMP
(46)/EGMP-4 (5)/ PC1 (0.04) DBTD DBP (0.3) HALS Example II-2 3-MBMA
(5)/PRX (5) (0.1) (0.1) Comparative -- XDI (36) DPMP (50)/PRX (14)
-- DBTD DBP (0.3) HALS Example II-3 (0.1) (0.1)
TABLE-US-00006 TABLE 6 Maximum absorption wavelength Color optical
Color fading rate No. (.lamda.max) density (second) HL
Moldability-1 Cloudiness-1 Moldability-2 Cloudiness-2 Example II-1
579 0.90 54 80 1 1 1 1 Example II-2 580 0.91 49 79 1 1 1 1 Example
II-3 589 0.84 55 97 1 1 2 2 Example II-4 585 0.70 60 93 1 1 1 1
Example II-5 578 0.71 54 100 1 1 2 1 Example II-6 584 0.58 52 85 1
1 1 2 Example II-7 -- -- -- 105 1 1 1 2 Example II-8 588 0.88 50 75
1 1 1 1 Comparative 576 0.90 48 75 1 1 4 1 Example II-1 Comparative
584 0.88 48 73 1 1 3 3 Example II-2 Comparative -- -- -- 85 1 2 3 4
Example II-3
Example I-12
[0592] A homogeneous liquid (optical composition) was prepared by
mixing each component according to the following formulation. Each
blending amount is shown in Table 7.
Formulation:
[0593] (A) Polyrotaxane: 12 parts by mass of AI-1
[0594] (B) Polyisocyanate compound: 37 parts by mass of XDI
[0595] (C) Poly(thi)ol compound: 38 parts by mass of DPMP, [0596]
Mono(thi)ol compound: 13 parts by mass of 1-DT
[0597] (D) Photochromic compound: 0.04 part by mass of PC1
[0598] (F) Polymerization curing accelerator: 0.001 part by mass of
DBTD: dibutyltin dilaurate (based on a total amount of the
mixture)
[0599] (Other blends): 0.1 part by mass of HALS
[0600] A photochromic laminate was obtained according to a coating
method by using the optical composition. A polymerization method is
described below.
[0601] As an optical base material, a thiourethane-based plastic
lens having a center thickness of about 2 mm, a spherical power of
-6.00 D, and a refractive index of 1.60 was arranged. In addition,
with regard to this thiourethane-based plastic lens, alkali etching
was applied thereto in advance at 50.degree. C. for 5 minutes by
using a 10% sodium hydroxide aqueous solution, and then the
resulting material was sufficiently washed with distilled
water.
[0602] A photochromic coating composition was added dropwise onto a
surface of the plastic lens rotated at 2,000 rpm by using Spin
Coater (1H-DX2, manufactured by MIKASA, Co., Ltd.). Then, a
photochromic laminate was obtained by heating the resulting
material at 120.degree. C. for 1 hour to cause polymerization
curing. A film thickness of a photochromic layer was about 30
.mu.m.
[0603] In the photochromic laminate obtained, a maximum absorption
wavelength was 586 nm, color optical density was 0.93, a color
fading rate was 50 seconds, Vickers hardness was 7, moldability-1
was 1 and cloudiness-1 was 1. Moreover, moldability and cloudiness
of the photochromic cured body (10 mm-thick) were evaluated. As a
result, moldability-2 was 1, and cloudiness-2 was 1. In addition,
the maximum absorption wavelength, the color optical density, the
color fading rate, the moldability-1 and the moldability-2, and the
cloudiness-1 and the cloudiness-2 were evaluated by the same
methods as the methods in Example 1 or the like, and the Vickers
hardness was evaluated by the method described below. These
measured values were shown in Table 8.
[0604] (9) Vickers hardness: Vickers hardness of the photochromic
layer obtained was measured using Micro Vickers Hardness Testing
Machine PMT-X7A (manufactured by Matsuzawa Co., Ltd.). The hardness
was evaluated by using a rectangular pyramid-type diamond indenter
as an indenter and under conditions of a load of 10 gf and an
indenter's retention time of 30 seconds. Measurements four times in
total were carried out, a first value having a large measurement
error was excluded, and the measurement results were shown in terms
of a mean value of measurements three times.
Example II-9
[0605] A photochromic cured body was prepared in the same manner as
in <Example I-12> except that a photochromic optical
composition having a formulation shown in Table 7 was used, and was
evaluated. The results were shown in Table 8.
TABLE-US-00007 TABLE 7 (A) Component (B) Component (C) Component
Other No. (parts by mass) (parts by mass) (parts by mass) (D)
Component (F) Component blends Example I-12 AI-1 (12) XDI (37) DPMP
(38)/1-DT (13) PC1 (0.04) DBTD HALS (0.001) (0.1) Example II-9
AII-1 (9) XDI (46) PEMP (35)/PGME10 (10) PC1 (0.04) DBTD HALS
(0.001) (0.1)
TABLE-US-00008 TABLE 8 Maximum absorption Color Color wavelength
optical fading rate Vickers No. (.lamda.max) density (second)
Moldability-1 Cloudiness-1 Moldability-2 Cloudiness-2 hardness
Example I-12 586 0.93 46 1 1 1 1 7 Example II-9 593 0.85 49 1 1 1 1
9
[0606] As is evident from the Examples and the Comparative Examples
described above, the cured body obtained by polymerizing the
optical composition according to the present invention has
excellent moldability and mechanical strength, and further reduced
cloudiness. Moreover, when the photochromic compound is added
thereto, the cured body is excellent in the photochromic
characteristics in addition to the physical properties described
above.
[0607] In contrast, in Comparative Examples I-1 and 1-2, while the
photochromic characteristics, the moldability-1, the cloudiness-1
and the like were satisfactory, the evaluation results of the
moldability-2 and the cloudiness-2, which were severer, were
insufficient. Moreover, also in Comparative Example 3, the
evaluation results of the moldability-2 and the cloudiness-2 were
insufficient.
[0608] Moreover, the optical composition according to the present
invention can also be applied to the coating method.
REFERENCE SIGNS LIST
[0609] 1: Polyrotaxane [0610] 2: Axle molecule [0611] 3: Cyclic
molecule [0612] 4: Bulky end group [0613] 5: Side chain having a
secondary or tertiary hydroxyl group
* * * * *